Beruflich Dokumente
Kultur Dokumente
Prepared by the
Undergraduate Education Subcommittee
of the
Center for Chemical Process Safety
and
THE
CENTER FOR CHEMICAL PROCESS SAFETY
OF THE
AMERICAN INSTITUTE OF CHEMICAL ENGINEERS
3 Park Avenue, New York, NY 10016-5901
ISBN 0-8169-0853-2
COPYRIGHT STATEMENT
Copyright 2002
American Institute of Chemical Engineers
3 Park Avenue
New York, NY 10016-5901
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any means, electronic, mechanical, photocopy,
recording, or otherwise, except for classroom use, without the prior permission of the
copyright owner.
ISBN 0-8169-0853-2
It is sincerely hoped that the information presented in this document will lead to an even
more impressive record for the entire chemical industry; however, the American Institute
of Chemical Engineers, its consultants, The Center for Chemical Process Safety (CCPS)
Subcommittee members, their employers, their employers officers and directors,
Authors Universities, and their members of the faculty, and the Authors disclaim making
or giving any warranties or representations, express or implied, including those with
respect to fitness, intended purpose, use or merchantability and/or correctness or
accuracy concerning the content of the information presented in this document. As
between (1) American Institute of Chemical Engineers, its consultants, CCPS
Subcommittee members, their employers, their employer's officers and directors,
Authors Universities, members of their faculty, their assistants and consultants, and the
Authors, and (2) the user of this document, the user accepts any legal liability or
responsibility whatsoever for the consequence of its use or misuse.
ii
ACKNOWLEDGEMENTS
The enclosed problem set is for the use in the education of undergraduate
chemical engineering students. This SACHE product was prepared by Ronald J. Willey,
Daniel A. Crowl, J.Reed Welker and Ron Darby with the direction and guidance of the
Undergraduate Education Committee (UEC) of the Center for Chemical Process Safety
(CCPS). This package was prepared for use by SACHE (Safety and Chemical
Engineering Education) members. CCPS appreciates the work by the authors and the
direction and guidance of the Undergraduate Education Committee.
Undergraduate Education Committee of CCPS
iii
PREFACE
1
Michael R. Lindeburg, P.E., Engineering-in-Training Reference Manual, 8th ed.,
Professional Publications, Inc., Chapt 63.
iv
GLOSSARY
This glossary defines many of the terms used on Material Safety Data Sheets (MSDS). It
also explains some of the significance of the terms related to safety, health, and loss
prevention. The glossary can provide substantial assistance in understanding terms
commonly used by safety and health professionals.
Importance: How much and how long Importance: Asphyxiation is one of the
one is exposed to a chemical is the pnncipal potential hazards of working in
cntical factor to how adverse the health confined spaces.
effects will be.
BOILING POINT The temperature at
ACUTE TOXICITY The adverse which a liquid changes to a vapor stare,
(acute) effects resulting from a single at a given pressure; usually expressed in
dose or exposure to a substance. degrees Fahrenheit at sea level pressure
(760 mrnHg, or one atmosphere). For
Importance: Ordinarily used to denote mixtures, the initial boiling point or the
effects in expenmental animals. boiling range may be given.
v
on the MSDS.
CHRONIC TOXICITY Adverse
C.A.S. NUMBER Chemical Abstracts (chronic) effects resultingfrom repeated
Service Number. doses of or exposures to a substance
over a relatively prolonged period of
Importance: C.A.S. Numbers are used time.
on MSDS's to identify specific
chemicals. Importance: Ordinarily used to denote
effects in experimental animals.
cc Cubic centimeter; a volume
measurement in the metric system, equal CO Carbon monoxide, a colorless,
in capacity to 1 milliliter (ml). One quart odorless, flammable and very toxic gas
is about 946 cubic centimeters. produced by the incomplete combustion
of carbon; also a byproduct of many
CHEMICAL FAMILY A group of chemical processes.
single elements or compounds with a
common general name. Example: CO2 Carbon dioxide, a heavy, colorless
acetone, methyl ethyl ketone, and methyl gas, produced by the combustion and
isobutyl ketone are of the "ketone" decomposition of organic substances
family; acrolein, furfural, and and as a by-product of many chemical
acetaldehyde are of the "aldehyde" processes. C02 will not burn and is
family. relatively non-toxic (although high
concentrations, especially in conf ned
Importance: Elements or compounds spaces, can create hazardous oxygen-def
within a chemical family generally have cient environments.)
similar physical and chemical
characteristics. Importance: CO and CO2 are often
listed on MSDS's as hazardous
CHEMTREC Chemical Transportation decomposition products.
Emergency Center; a national center
established by the Chemical COMBUSTIBLE A term used to
Manufacturers Association in classify certain liquids that will burn, on
Washington, D.C. in 1970, to relay the basis of flash points. Both the
pertinent emergency information National Fire Protection Association
concerning specific chemicals. (NFPA) and the Department of
Transportation (DOT) define
Importance: Chemtrec has an combustible liquids as having a flash
emergency 24 hour toll free telephone point of 100/F (37.8/C) or higher. See
number (800-424-9300). also, Flammable.
vi
Class IIIB: Those having flash points at effects in experimental animals.
or above 200/F.
EMERGENCY AND F1RST AID
CONCENTRATION The relative PROCEDURES Actions that should be
amount of a substance when combined taken at the time of a chemical exposure
or mixed with other substances. before trained medical personnel arrive.
Examples: 2 ppm Xylene in air, or a 50
percent caustic solution. Importance: These procedures may
lessen the severity of an injury or save a
Importance: The effects of person's life if done immediately
overexposure depend on the following a chemical exposure .
concentration or dose of a hazardous
substance. EPA U. S. Environmental Protection
Agency: Federal agency with
CORROSIVE As defined by DOT, a environmental protection regulatory and
corrosive material is a liquid or solid enforcement authority.
that causes visible destruction or
irreversible changes in human tissue at Importance: EPA regulations must be
the site of contact on-- in the case of met for the disposal of hazardous
leakage from its packaginga liquid matenals, as well as in spill situations.
that has a severe corrosion rate on steel.
EVAPORATION RATE A number
Importance: A corrosive material showing how fast a liquid will
requires different personal protective evaporate.
equipment to prevent adverse health
effects. Importance: The higher the evaporation
rate, the greater the nsk of vapors
DECOMPOSITION Breakdown of a collecting in the workplace. The
material or substance (by heat. chemical evaporation rate can be useful in
reaction, electrolysis, decay, or other evaluating the health and fire hazards of
processes) into parts or elements or a material.
simpler compounds.
FLAMMABILITY LIMITS The range
Importance: Decomposition products of gas or vapor amounts in air that will
often present different hazards than the burn or explode if a flame or other
original material . ignition source is present.
DERMAL Used on or applied to the Importance: The range represents an
skin. unsafe gas or vapor mixture with air that
may ignite or explode. Generally, the
Importance: Dermal exposure, as well wider the range the greater the fire
as inhalation exposure, must be potential. Also, see LEL, LFL, UEL,
considered to prevent adverse health UFL.
effects.
FLAMMABLE A Flammable Liquid is
DERMAL TOXICITY Adverse effects defined by NFPA and DOT as a liquid
resulting from skin exposure to a with a flash point below 100/F (37.8/C).
substance. Also referred to as
"Cutaneous toxicity." Importance: Flammable liquids provide
ignitable vapor at room temperatures and
Importance: Ordinarily used to denote must be handled with caution.
vii
Precautions such as bonding and see also Local Exhaust.
grounding must be taken. Flammable
liquids are: Class I liquids md may be Importance: Adequate ventilation is
subdivided as follows: necessary to prevent adverse health
effects from exposures to hazardous
Class IA: Those having flash points matenals and vapor accumulations that
below 73/F and having a boiling point can be a fire hazard.
below 100/F.
g Gram; a metric unit of weight. One
Class IB: Those having flash points U.S. ounce is about 28.4 grains.
below 73/F and having a boiling point at
or above 100/F. g/kg Grams per kilogram; an expression
of dose used in oral and dermal
Class IC: Those having flash points at or toxicology testing to indicate the grams
above 73/F and below 100/F. of substance dosed per kilogram of
animal body weight. See also "kg."
FLASH POINT The lowest temperature
at which vapors above a liquid will Importance: A measure of the toxicity
ignite. There are several flash point test of a substance.
methods and flash points may varyfor
the same material depending on the HAZARDOUS MATERIAL in a
method used. Consequently so the test broad sense a hazardous material is any
method is indicated vhen theflash point substance or mixture of substances
is given (150/ PMCC 200/ TCC etc. ) A having properties capable of
closed cup type test is used producing-adverse effects on the health
mosttrequentlyfor regulatory purposes. or safety of a human being.
Flash point test methods:
Importance: Knowing what a
Cleveland Open Cup (CC) hazardous material is and what matenals
are hazardous is important in preventing
Penskv Manens Closed Cup (PMCC) adverse health or safety effects.
Setaflash Closed Tester (SETA)
IDLH IDLH or Immediately dangerous
Tag Closed Cup (TCC) to life or health means an atmospheric
Tag Open Cup (TOC) concentration of any toxic, corrosive or
asphyxiant substance that poses an
Importance: The lower the flash point immediate threat to life or would cause
temperature of a liquid, the greater the irreversible or delayed adverse health
chance of a fire hazard. effects or would interfere with an
individual's ability to escape from a
Formula The conventional scientific dangerous atmosphere.
designation for a material (water is H2O (http://www.osha.gov/)
sulfuric acid is H2S04 Sulfur dioxide is
SO2. etc.) Importance: Explosure to
concentrations greater than the IDLH for
Importance: Chemical formulas any length of time can mean serious
identify specific materials. injury including death. As a safety
margin, the Standards Completion
GENERAL EXHAUST A system for Program IDLH values were based on the
exhausting air containing effects that might occur as a
contaminantsfrom a general work area. consequence of a 30-minute exposure.
viii
However, the 30-minute period was IRRITANT A substance which by
NOT meant to imply that workers should contact in sufficient concentration for a
stay in the work environment any longer sufficient period of time will cause an
than necessary, in fact, EVERY inflammatory response or reaction of the
EFFORT SHOULD BE MADE TO eye skin or respiratory system. The
EXIT IMMEDIATELY! (Source: contact may be a single exposure or
http://www.cdc.gov/niosh/npg/pgintrod. multiple explosures. Some primary
html) irritants: chromic acid, nitric acid,
sodium hydroxide, calcium chloride,
INCOMPATIBLE Materials which amines, chlorinated hydrocarbons,
could cause dangerous reactions from ketones, alcohols.
direct contact with one another are
described as incompatible. Importance: Knowing that a substance
is an instant allows you to be aware of
Importance: on a MSDS, incompatible the signs and symptoms of
materials are listed to prevent dangerous overexposure.
reactions in the handling and storage of
the material. kg Kilogram; a metric unit of weight
about 2.2 U.S. pounds See also g/kg
INGESTION The taking of a substance g and mg.
through the mouth.
L Liter; a metric unit of capacity. A U.S.
Importance: A route of exposure to a quart is about 9/10 of a liter.
hazardous matenal.
LC Lethal Concentration: A
INGREDIENTS A listing of chemicals concentration of a substance being
that are in a mixture. tested which will kill a test animal.
Importance: Knowing exactly what LC50 Lethal Concentration 50; The
chemicals and how much of each is in a concentration of a material in air which
mixture helps you to understand the on the basis of laboratory tests is
potential hazard a mixture presents. expected to kill 50 percent of a group of
test animals when administered as a
INHALATION The breathing in of a single exposure (usually or 4 hours).
substance in theform of a gas vapor The LC50 is expressed as parts of
fume mist or dust. material per million parts of air by
volume (ppm)for gases and vapors or as
Importance: A route of exposure to a micrograms of material per liter of air
hazardous matenal . (glL) or milligrams of material per
cubic meter of air (mg/m3) for dusts and
INHIBITOR A chemical which is added mists as well as for gases and vapors.
to another substance to prevent an
unwanted chemical change from Importance: Both are measures of the
occurring. toxicity of a substance.
ix
laboratory tests is expected to kill 50% MELTING POINT The temperature at
of a group of test animals. The LD50 dose which a solid substance changes to a
is usually expressed as milligrams or liquid state. For mixtures, the melting
grams of material per kilogram of range may be given.
animal body weight (mg/kg or g/kg).
Importance: The physical state of a
Importance: Both are measures of the substance is critical in assessing its
toxicity of a substance. hazard potential, route of exposure and
method of control.
LEL OR LFL Lower Explosive Limit or
Lower Flammable Limit of a vapor or mg Milligram; a metric unit of weight.
gas; the lowest concentration (lowest There are 1,000 milligrams in 1 gram (g)
percentage of the substance in air) that of a substance.
will produce a flash of fire when an
ignition source (heat, arc, or flame) is mg/kg Milligrams per kilogram; an
present. See also, "UEL." expression of toxicological dose. see
also, g/kg.
Importance: At concentrations lower
than the LEL/LFL, the mixture is too Importance: A measure of the toxicity
"lean" to burn. of a substance .
LOCAL EXHAUST A system for mg/m3 Milligrams per cubic meter; a
capturing and exhausting contaminants unit of measuring concentrations of
from the air at the point where the dusts, gases, or mists in air.
contaminants are produced (welding,
grinding, sanding, dispersion Importance: The effects of
operations). See also, "General overexposure depend on the
exhaust." concentration or dose of a hazardous
substance .
Importance: Adequate ventilation is
necessary to prevent adverse health mL Milliliter; a metric unit of capacity,
effects from exposures to hazardous equal in volume to 1 cubic centimeter
materials and prevent vapor (cc) or about 1/16 of a cubic inch. There
accumulations that can be a fire hazard. are 1,000 milliliters in 1 liter (L).
MATERIAL IDENTIFICATION The mm Hg Millimeters (mm) of Mercury
name of a chemical. It may be a trade (Hg); a unit of measurement for low
name, chemical name or any other name pressures or partial vacuums .
a chemical is known by. On a MSDS this
section also includes the name, address, Importance: Vapor pressures are
and emergency telephone number of the expressed in mm Hg.
distributing chemical company.
MUTAGEN A substance or agent
Importance: Proper identification of a capable of altenng the genetic material
chemical allows an employee to get in a living cell.
additional health hazard and safety
information. Importance: if a substance is known to
be a mutagen, a potential health hazard
m3 Cubic meter; a metric measure of exists, and special protection and
volume, about 35.3 cubic feet or 1.3 precaution sections should be checked
cubic yards. on the MSDS.
x
NIOSH National Institute for OXIDIZING AGENT, OXIDIZER A
Occupational Safety and Health of the chemical or substance which brings
Public Health Service, U.S. Department about an oxidation reaction. The agent
of Health and Human Services (DHHS). may (I) provide the oxygen to the
substance being oxidized (in which case
Importance: Federal agency the agent has to be oxygen, or contain
whichamong other activitiestests oxygen), or (2) it may receive electrons
and certifies respiratory protective being transferred from the substance
devices, recommends occupational undergoing oxidation. DOT defines an
exposure limits for various substances oxidizer or oxidizing material as a
and assists in occupational safety and substance which yields oxygen readily to
health investigations and research. stimulate combustion (oxidation) of
organic matter.
NOx Oxides of Nitrogen; undesirable
air pollutants. Importance: if a substance is listed as
an oxidizer on the MSDS, precautions
Importance: Often listed on a MSDS as must be taken in the handling and
a hazardous decomposition product. storage of the substance. Keep away
from flammables and combustibles.
OLFACTORY Relating to the sense of
smell. PEL Permissible Exposure Limit; an
exposure established by OSHA
Importance: The olfactory organ in the regulatory authority. May be a Time
nasal cavity is the sensing element that Weighted Average (TWA) limit or a
detects odors and transmits information maximum concentration exposure limit.
to the brain through the olfactory nerves. See also, Skin
This sense of smell is a "built in" vapor
detector. Importance: if a PEL is exceeded, a
potential health hazard exists, and
ORAL Used in or taken into the body corrective action is necessary.
through the mouth.
POISON, CLASS A A DOT term for
Importance: A route of exposure to a extremely dangerous poisons, that is,
hazardous material. poisonous gases or liquids of such
nature that a very small amount of the
ORAL TOXICITY Adverse effects gas, or vapor of the liquid, mixed with
resulting from taking a substance into air is dangerous to life. Some examples:
the body via the mouth. phosgene, cyanogen, hydrocyanic acid,
nitrogen peroxide .
Importance: Ordinarily used to denote
effects in experimental animals. POISON, CLASS B A DOT term for
liquid, solid, paste, or semisolid
OSHA Occupational Safety and Health substancesother than Class A poisons
Administration of the U.S. Department or irritating materialswhich are
of Labor. known (or presumed on the basis of
animal tests) to be so toxic to man as to
Importance: Federal agency with safety afford a hazard to health during
and health regulatory and enforcement transporation.
authorities for most U.S. industry and
business. Importance: if a substance is known to
be a poison, health and safety hazards
xi
exist and special protection and
precaution sections should be checked Importance: Knowledge of reactions
on the MSDS. can prevent unsafe chemical changes.
POLYMERIZATION A chemical REACTIVITY A description of the
reaction in which one or more small tendency of a substance to undergo
molecules combine to form larger chemical reaction with itself or other
molecules. A hazardous polymerization materials with the release of energy.
is such a reaction which takes place at a Undesirable effectssuch as pressure
rate which releases large amounts of buildup, temperature increase,
energy. formation of noxious, toxic, or corrosive
by-productmay occur because of the
Importance: if hazardous reactivity of a substance to heating,
polymerization can occur with a given burning, direct contact with other
matenal, the MSDS usually will list materials or other cond itions in use or
conditions which could start the reaction in storage.
and the time penod before any contained
the inhibitor is used up. Importance: Knowledge of what
conditions to avoid can prevent failsafe
ppm Parts per million: a unit for chemical reactions.
measuring the concentration of a gas or
vapor in airparts (by volume) of the REDUCING AGENT in a reduction
gas or vapor in a million parts of air. reaction (which always occurs
Also used to indicate the concentration simultaneously with an ovulation
of a particular substance in a liquid or reaction) the reducing agent is the
solid . chemical or substance which (1)
combines with oxygen, (2) loses
Importance: The effects of electrons in the reaction. See also,
overexposure depend on the "Oxidizing Agent."
concentration or dose of a hazardous
substance. Importance: if a matenal is listed as a
reducing agent on the MSDS,
ppb Parts per billion; a unit for precautions must be taken in the
measuring the concentration of a gas or handling and storage of the substance.
vapor in airparts (by volume) of the Keep separate from oxidizing agents.
gas or vapor in a billion parts of air.
Usually used to express measurement of RESPIRATORY SYSTEM The
extremely low concentrations of breathing system; includes the lungs and
unusually toxic gases or vapors. Also air passages (trachea or "windpipe,"
used to indicate the concentration of a larynx, mouth, and nose) to the air
particular substance in a liquid or solid. outside the body, plus the associated
nervous and circulatory supply.
Importance: The effects of
overexposure depend on the Importance: Inhalation is the most
concentration or dose of a hazardous common route of exposure in the
substance. occupational workplace.
REACTION A chemical transformation SENSITIZER A substance which on
or change; the interaction of two or first exposure causes little or no reaction
more substances to form new in man or test animals, but which on
substances. repeated exposure may cause a marked
xii
response not necessarily limited to the SPECIAL PRECAUTIONS
contact site. Skin sensitization is the Instructions that describe proper
most common form of sensitization in the handling and storage procedures
industrial setting, although respiratory specific to that material.
sensitization to a few chemicals is also
known to occur. Importance: Following these
procedures would prevent excessive
Importance: Knowing that a substance employee exposure. These procedures
is a sensitizer allows you to be aware of tell you additional information needed to
the signs and symptoms of handle the material safely.
overexposure.
SPECIAL PROTECTION
"SKIN" A notation, sometimes used INFORMATION A description of
with PEL or TLV exposure data; engineering precautions and personal
indicates that the stated substance may protection that should be provided when
be absorbed by the skin, mucous working with a chemical in order to
membranes, and eyeseither by reduce an employee's exposure.
airborne or by direct contactand that
this additional exposure must be Importance: Reducing the potential for
considered part of the total exposure to exposure reduces the nsk to health and
avoid exceeding the PEL or TLV for that safety.
substance.
SPECIFIC GRAVITY The weight of a
Importance: Even if workplace material compared to the weight of an
concentrations of a chemical do not equal volume of water;an expression of
exceed the TLV or PEL, the risk to the density (or heaviness) of the material
health may be severe because breathing Example: if a volume of a material
and skin contact are combined. Skin weighs 8 pounds, and an equal volume
protection is advised. of water weighs 10 pounds, the material
is said to have a specific gravity of 0.8
SKIN SENSITIZER See Sensitizer.
8 1b/10 lb = 0.8
SKIN TOXICITY See Dermal
Toxicity. Importance: Insoluble matenals with
specific gravity of less than 1.0 will float
SOLUBILITY IN WATER A term in (or on) water. Insoluble matenals with
expressing the percentage of a material specific gravity greater than 1.0 will sink
(by weight) that will dissolve in water at (or go to the bottom) in water. Most
ambient temperature. flammable liquids have specific gravity
less than 1.0 and, if not soluble, will
Importance: Solubility information can float on wateran important
be useful in determining spill cleanup consideration for fire suppression and
methods and fire-extinguishing agents spill clean-up.
and methods for a material.
SPILL OR LEAK PROCEDURES
SOx Oxides of Sulfur; undesirable air Steps that should be taken if a chemical
pollutants. spill or leak occurs
xiii
hazardous concentrations of the normal 8-hour workday or 40-hour work
chemical, reduces the nsk of creating an week
environmental pollution problem and
conforms with local, state and federal TLV-STEL: The Short-Term Exposure
regulations. Limit, or maximum concentration for a
continuous 15 minute exposure period
STABILITY An expression of the (maximum of four such periods per day
ability of a material to remain with at least 60 minutes between
unchanged exposure periods, and provided that the
daily TLV-TWA is not exceeded)
Importance: For MSDS purposes, a
material is stable if it remains in the TLV-C: The Ceiling exposure limitthe
same form under expected and concentration that should not be
reasonable conditions of storage or use. exceeded even instantaneously
Conditions which may cause instability
(dangerous change) are statedfor TLVs are reviewed and revised
example, temperatures above 150/F, annually where necessary by the ACGIH
shock from dropping .
Importance: if a TLV is exceeded, a
STEL Short Term Exposure Limit; potential health hazard exists and
ACGIH terminology See also, corrective action is necessary. Also see
TLV-STEL. Skin relative to TLV's.
xiv
ignition source (heat, arc, or flame) is and Local Exhaust
present
xv
TABLE OF CONTENTS
COPYRIGHT STATEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
ACKNOWLEDGEMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
PREFACE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
GLOSSARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
xvi
Safety Problems for a Course in Stoichiometry
S-1 The minimum ignition energy (MIE) is the minimum energy input required to
initiate combustion in a flammable mixture. For flammable gases it is typically
0.1 mJ and for dusts it is typically 10 mJ, although substantial variation can be
expected with specific materials.
The mass of a penny is typically 2.6 gms. How far must this penny be raised to
contain potential energy equivalent to 0.1 mJ?
S-2 Calculate the number of liters per year of liquid that can be transported through
the following pipe sizes assuming a constant liquid velocity of 1 meter/sec.
a) 3 cm ID
b) 5 cm ID
c) 25 cm ID
d) 50 cm ID
Comment on the magnitude of the result and the necessity for large pipe sizes in a
chemical plant.
S-3 Calculate the number of kg per year of ideal gas that can be transported through
the following pipe sizes assuming a gas velocity of 3 meters/sec, a pressure of 689
kPa gauge, a temperature of 25oC, and a molecular weight of 44.
a) 3 cm ID
b) 5 cm ID
c) 25 cm ID
d) 50 cm ID
Comment on the magnitude of the result and the necessity for large pipe sizes in a
chemical plant.
S-4 Large storage tanks are only capable of withstanding very low pressures or
vacuums. Typically they are constructed to withstand no more than 20.3 cm of
water gauge pressure and 6.3 cm of water gauge vacuum.
A particular tank is 10-m in diameter.
a) If an 80 kg person stands in the middle of the tank roof, what is the
resulting pressure (in Pa) if the person's weight is distributed across the
entire roof?
b) If the roof were flooded with 20.3 cm of water (equivalent to the
maximum pressure), what is the total weight (in kg) of the water?
S-5 A low pressure storage tank is padded with nitrogen. The purpose of the padding
is to remove oxygen and to prevent a flammable atmosphere from forming in the
tank due to the presence of a flammable liquid.
A particular tank is padded with nitrogen to a total pressure of 0.03 psig.
If the tank is at 55oF in the morning and is heated to 85oF in the afternoon, what
will be the final pressure in the tank? If the maximum design pressure of the tank
is 8 inches of water gauge, has the design pressure been exceeded?
1
S-6 How much acetone liquid (in mls) is required to produce a vapor concentration of
200 ppm (parts per million) by volume in a room of dimensions 3 x 4 x 10
meters? The temperature is 25oC and the pressure is 1 atm. The following
physical property data are available for acetone:
Molecular weight: 58
Specific gravity: 0.781
S-7 The lower flammability limit (LFL) for a gas is the minimum concentration of the
gas, in air, below which there is too little fuel to support combustion. For propane
the LFL is 2.1%.
a) How many kg of propane are required to fill a room of dimensions 10 x 10
x 3 m if the final mixture is stoichiometric with air?
b) What is the volume percent concentration at the stoichiometric
concentration?
c) How many kg of propane are required to fill the same room to a
concentration equal to the LFL?
For all cases assume a temperature of 25oC and a pressure of 1 atm.
S-8 The flash point is the temperature below which a liquid is unable to produce
enough vapor to support a combustion in air. For flammable materials mixed
with a non-flammable material (such as water), the flash point of the mixture will
occur at a temperature at which the partial pressure of the flammable component
is equal to the saturation vapor pressure of the pure component at the flash point.
Acetone is used as a solvent in a laboratory. There is some concern about the fire
hazards associated with acetone. One solution is to dilute the pure acetone with
water, thus increasing the flash point and reducing the fire hazard.
Acetone has a reported flash point of 0oF. It's vapor pressure is represented by the
Antoine equation:
Where
is the saturation vapor pressure (mm Hg)
T is the absolute temperature, K.
S-9 The liquid level in a tank 10 meters in height is determined by measuring the
pressure at the bottom of the tank. The level gauge was calibrated to work with a
liquid having a specific gravity of 0.9. If the usual liquid is replaced with a new
liquid with a specific gravity of 0.8, will the tank be overfilled or underfilled? If
the actual liquid level is 8 meters, what is the reading on the level gauge? Is it
possible that the tank will overflow without the level gauge indicating the
situation?
2
S-10 The column shown below was used to strip low-volatile materials from a high
temperature heat transfer fluid. During a maintenance procedure, water was
trapped between the valves shown on the figure. During normal operation, the
upper valve was opened and the hot oil came in contact with the cold water. The
result was almost sudden vaporization of the water, followed by considerable
damage to the column.
Consider liquid water at 25oC and 1 atm. How many times does the volume
increase if the water is vaporized into vapor at 100oC and 1 atm?
Column
Hot oil
S-11 Inerting is a procedure by which oxygen is removed from a tank or process vessel
using an inert gas, such as nitrogen.
One procedure for inerting pressure vessels is to pressurize the vessel with
nitrogen and then vent the tank back to atmospheric pressure. The cycle is
repeated until the oxygen concentration is lowered to satisfactory levels.
a) Show that, using a source of pure nitrogen, the oxygen concentration at
the end of the jth pressurization cycle is given by
Where
yj is the oxygen concentration at the end of the
jth cycle.
yo is the initial oxygen concentration,
PL is the low pressure in the cycle,
PH is the high pressure in the cycle, and
b) Show that the total nitrogen used for the procedure is given by
Where
is the total nitrogen used,
V is the total vessel volume,
Rg is the ideal gas constant, and
3
T is the absolute temperature.
S-12 The equations developed in problem S-11 apply to pressurization using a source
of pure nitrogen. Show that for a source of nitrogen containing oxygen at a
concentration of yoxy, the concentration at the jth pressurization cycle is given by,
If the nitrogen supply in problem S-11 contains 0.5% oxygen, how many cycles
are now required?
4
Safety Problems for a Course in Thermodynamics
5
make an estimate of the energy released following failure of a fire extinguisher.
The energy release might then be used to estimate the damage, although we will
not carry the analysis that far.
6
T-4 Thermodynamics Principle: Adiabatic expansion of high pressure liquid to gas
Problem: The thermostat on a 40-gal water heater fails and the water is
heated to a much higher temperature than normal. The relief valve
also fails to operate and the water tank ruptures. The tank ruptures
when the water reaches 300F and you may assume the process of
expansion following the tank rupture to be adiabatic and
reversible. What is the TNT equivalent of the explosion if TNT
does 2000 Btu/lb of work when it explodes? (Most home water
heaters are 40 gal or larger.)
7
estimated from thermodynamic data for the liquid and an estimate of the
temperature range over which the liquid will be stored.
8
T-7 Thermodynamics Principle: Adiabatic flash of a superheated liquid
Background: Safety does not always apply only to the chemical plants where
people work. People also have to travel to their jobs. Thermodynamic analyses
do not always apply only to problems in the chemical plant. They also apply to
ordinary problems at home and during activities at other places. One of the most
common causes of accidental death is automobile accidents. Well-designed
brakes are an important part of the automobile. Under heavy usage, the brakes
may overheat and fail. An estimation of the temperature of the brake components
is helpful in brake design.
9
Problem: Most chemical engineering problems involving the energy balance
neglect the kinetic and potential energy terms, but those terms are
not always negligible. In addition, the energy balance can be used
to solve a number of other kinds of problems. For example, a car
has disk brakes. The disks are steel, weigh about 15 lb, and have a
heat capacity of about 0.11 Btu/lb-F. The brake pads are a
composite material. There are two pads per wheel, and the pads
weigh about one pound each and have a heat capacity of about 0.2
Btu/lb-F. If the driver makes a panic stop from 55 mi/hr and the
car weighs 3600 lb, estimate the maximum temperature that might
be reached by the brake disks and pads. The brake disks and pads
are initially at 75 /F.
Background: The density (or specific volume) of a liquid does not change very
much when the pressure on the liquid is changed. Neither does the density
change much when small temperature changes occur. However, if the liquid is
confined, a small rise in temperature will cause a very large change in pressure. If
the liquid is confined in a pipe, and if there is no vapor space in the pipe, the
pressure can easily become so large that the pipe will crack or burst. There is not
much data in the literature on the density of compressed liquids because the effect
is small enough to neglect for most purposes. However, pressure and temperature
effects must sometimes be estimated for liquids. One of the ways we can estimate
the effect a higher temperature will have on a confined liquid is to calculate the
pressure required to keep the density of the liquid constant when the temperature
is increased. We can make the estimate using an equation of state if an equation
of state can be found that represents the liquid PVT behavior.
10
you decide to make the best estimate you can in a short time using
the Peng-Robinson equation of state. For this problem, you are to
calculate the pressure exerted by liquid benzene if its volume
remains constant at the specific volume at 5.5 /C and the liquid
temperature increases. Make the calculations for a temperature
range of 5.5 /C to 20 /C and plot the results. Is the pressure rise
high enough to cause the pipe to rupture? Compare the results of
your plot with any data you can find in the literature. (A pipe
rupture followed by a spill of several hundred barrels of benzene
actually occurred under circumstances similar to those described
here during the winter of 1995-96.)
Background: Many of the chemicals used in commerce and trade are toxic.
(Actually, many newspaper writers and television newscasters believe that the
word chemical should always be preceded by an adjective like hazardous,
toxic, or poisonous. If they are correct, we do a marvelous job of protecting
society from such effects.) If toxic chemicals are processed in a chemical plant, it
is possible that spills and leaks may occur. While our goal is to prevent all
releases, if they happen, we must protect workers from the toxic effects of the
chemicals. One method of protection is to provide a self-contained breathing
apparatus (SCBA) that will provide enough air for the worker to either control the
spill or to escape from the spill area. Common SCBA equipment is designed for
storing air under pressures of about 2200 psi or 4500 psi, and the air supply may
be sufficient for 30 minutes or 60 minutes. At such high pressures, air does not
behave like an ideal gas.
11
formed will expand rapidly, with explosive force. The phase change and
expansion are so rapid that the entire process is essentially adiabatic. The blast
damage can be substantial. The potential for such an explosion is not only
present for what we normally think of as hazardous materials. It also occurs for
such mundane materials as water. The danger also occurs under conditions where
no chemical processing occurs, so we must extend our vigilance to all situations
where danger might exist.
12
contains 16 gallons of gasoline.
a) The mole fraction of propane in the liquid mixture leaving the absorber.
b) The concentrations of both the liquid and vapor streams leaving the flash
drum.
The vapor pressures of propane and decane may be obtained from the
following equations, which are taken from The Properties of Gases and
Liquids by Reid, Prausnitz, and Sherwood (1977).
13
The vapor pressures are in mm Hg and the temperatures are in Kelvins. The
solution of the problem requires some extrapolation of the vapor pressures beyond
the range of best accuracy for the equations, but allows the problem to be worked
easily.
c) Describe how you would work this problem if you could not assume ideal
behavior.
14
mixture using 25 percent excess air provide the 1000C
temperature required? You may assume that the heat capacities
are constant (unless your instructor advises you otherwise), and the
following values apply:
Water, liquid 75
Acetone, liquid 129
Water, gas 38
Oxygen, gas 37
Nitrogen, gas 32
Carbon dioxide, gas 74
Problem: Acetylene is a very unstable gas that has a high positive heat of
formation. Because the heat of formation is positive, if the
acetylene decomposes, a large release of energy will occur.
Assume that you have acetylene contained by a pressure vessel at
25C and 100 psia pressure. If the acetylene decomposes, both the
temperature and the pressure will increase. Estimate the
temperature and pressure of the products if the reaction occurs
inside the storage vessel. Since the initial pressure is relatively
low and the final temperature high, you may assume that all gases
behave ideally. However, the heat capacities of the acetylene,
carbon, and hydrogen are not constant. Heat capacities and heats
of formation for these materials may be found in the Chemical
Engineers' Handbook. The reaction will be rapid enough that you
may assume it to be adiabatic.
15
T-16 Thermodynamics Principle: Dew point calculation
Problem: In the natural gas industry, peak demands for winter gas supply are
sometimes met by mixing propane and air together to produce a
mixture that has the same heat of combustion as natural gas.
Assume that such blending has taken place and that the propane-air
mixture has been blended with natural gas and is being distributed
through a pipeline to the customers. Severe safety problems can
occur if the propane condenses out of the propane-air-natural gas
mixture. Assume the blending process has resulted in a mixture
that is 70 mole percent methane, 7 mole percent ethane, 11 mole
percent propane, and the balance air. Then assume the gas
temperature can fall to - 20 /F in some parts of the pipeline.
Determine the highest pressure that the gas may be allowed to
reach before liquid begins to condense from the mixture. Also
determine the concentration of each of the components in the
liquid mixture that forms.
Problem: Determine the fraction of vapor and the composition of the vapor
16
and liquid phases when a feed mixture that originally contained 30
mole percent n-hexane, 20 mole percent cyclohexane, 30 mole
percent 2,2,4-trimethylpentane, and 20 mole percent n-decane is
brought to 100 /C and 1.0 atm. The vapor pressure equations for
these hydrocarbons may be given by the Antoine equation,
Component A B C
Background: Many chemicals are quite toxic. They can cause short term effects
such as acute poisoning or long term effects such as cancer. Some chemicals
have both effects. In order to keep such chemicals from endangering workers, the
Occupational Safety and Health Administration has promulgated rules that
specify safe exposure levels for workers. One of those safe exposure levels is the
Permissible Exposure Limit, or PEL. The PEL is a concentration of chemical in
the air to which a worker can be exposed for 40 hours per week throughout his
lifetime without either short-term or long-term ill effects. The PEL is primarily
defined for lifelong exposure, and is set at a low enough level to preclude any
health effect. Mixtures of chemicals may also occur, and methods have been
formulated to estimate the maximum concentrations that are allowable for
workers where mixed chemical exposure are found. The intended result is to
protect workers, but a side effect is to protect the public as well.
NO + O2 --------> NO2
Both of the oxides of nitrogen are quite toxic. The OSHA PEL for NO is
17
25 ppm and the PEL for NO2 is 3 ppm. Obviously, in any process where
air is heated to a high enough temperature, some of the oxides may form.
The problem is complicated by the fact that the reaction forming NO is
endothermic but the reaction in which NO is further oxidized to NO2 is
exothermic. Thus, the equilibrium concentrations of the two are driven in
opposite directions: conditions favoring formation of one do not favor the
formation of the other. (Other reactions, which we will not consider in
this problem, may also occur, so the results may differ substantially from
the results we get here. We simplify the problem to make it easier to
solve. We will ignore formation of other oxides of nitrogen.)
Assume that the oxides are formed from air, and that a catalyst is available
that will cause the reactions to come to equilibrium at all the temperatures
we consider. (In practice, we try to use such catalysts to reduce pollution
from automobile exhausts.) Calculate the equilibrium concentrations of
NO and NO2 at temperatures from 200 /C to 2000 /C.
If the sum
then the PEL for the mixture will be exceeded. Will the PEL for the
mixture be exceeded over the temperature range in question? If so, over
what temperature range will the PEL not be exceeded?
Background: Many flammable chemicals are stored as liquids in tanks that are
vented to the atmosphere. If air can flow freely into and out of the tank, the
vapor-air mixture above the liquid level can contain sufficient vapor to be
flammable. If ignited, an explosion and fire will result. If the chemical has a
sufficiently high vapor pressure at the storage temperature, the vapor-air mixture
will be too rich to burn. If the vapor pressure is low enough, the vapor-air
mixture will be too lean to burn. The term too rich means that the
concentration of fuel in the vapor space is higher than the upper flammable limit
(UFL). Too lean means the concentration of fuel is less than the lower
flammable limit (LFL). Flammability limits are usually measured for the fuel
vapor (or gas) in air at ambient conditions of about 25 /C and 1.0 atm. The limits
can change when the temperature or pressure change substantially, but most
concern is taken for ambient conditions, because most accidental spills occur at
ambient conditions.
Problem: The lower flammable limit (LFL) of methanol is 6.0 percent in air
18
and the upper flammable limit (UFL) is 36 percent in air. If
methanol is stored in a tank that is vented to the atmosphere, over
what temperature range will the equilibrium vapor-air mixture
above the methanol surface be flammable? The vapor pressure of
methanol is given in Lange's Handbook, 13th ed, as
Background: Most students of chemistry have been told that concentrated acids
are to be diluted by pouring the concentrated acid slowly into water. The reason
for pouring the acid into the water is that the mixing process is highly exothermic
and substantial temperature increases may occur. If the more dense acid is poured
into the water, it tends to sink to the bottom and the water solution can absorb
much of the energy generated during mixing. Even if the acid and water are
carefully mixed, the temperature may still rise enough to cause dangerous
conditions if the mixing is too fast and no cooling of the mixture is possible.
Problem: The mixing of two chemicals can result in a quite large increase in
temperature of the mixture over the temperatures of the
constituents. If the temperature increases enough, the liquid will
boil explosively, which can have serious safety consequences.
Assume that you are going to mix 500 lb of water at 80 /F and 500
lb of sulfuric acid, also at 80 /F. What will the final temperature of
the mixture be? Will the mixture be above the boiling point? Data
for this problem can be found in the Chemical Engineers'
Handbook.
T-21 Thermodynamics Principle: Freezing points of mixtures
19
solvent are initially liquids, the temperature at which solids will exist in
equilibrium with the liquid mixture depends on the liquid concentrations and
other liquid properties. We sometimes exploit this phenomenon of freezing point
depression.
Cyclohexane n-Octane
Solubility parameter, * (cal/cm3) 8.2 7.5
Liquid volume, VL (cm3/gmole) 109 164
)hf (J/gmole) 3080 20740
Normal melting point (K) 279.7 216.3
Cp, solid (J/gmole-K) 146 236
Cp, liquid (J/gmole-K) 150 241
20
Problem: The vapor pressure of ethanol can be estimated from the Antoine
equation
21
T-24 Thermodynamics Principle: Vapor-liquid equilibrium
Health and Safety Concept: Flash points and LFL for mixtures
Problem: You must estimate the flash point of a mixture of tert-butyl alcohol
and water that has 80 percent by weight tert-butyl alcohol. The
Chemical Engineers' Handbook contains data for the binary
system and shows that an azeotrope occurs at 760 mm Hg and
79.91 /C with a mole fraction of water of 0.3541. The flash point
of pure tert-butyl alcohol is found to be 52 /F. Using only this
information (and molecular weights and vapor pressures of the
pure materials), estimate the flash point of the solution.
Background: Many chemicals are toxic and must not be allowed to enter the air
or water. Considerable research has led to the estimation of the concentrations of
chemicals that can be tolerated by humans. The Permissible Exposure Limit
(PEL) is the concentration that workers can be legally exposed to for an eight-
hour period five days per week throughout their lifetime. The PEL is a time-
weighted average, so the instantaneous concentration may be higher than the
PEL. The Short Term Exposure Limit (STEL) is the concentration permitted by
law for exposures up to 15 minutes as many as four times per day, as long as there
is a period of one hour between exposures and the PEL is not exceeded. The
ceiling concentration must never be exceeded. These concentrations are
estimated based on tests made with animals and extrapolated to humans. They
are also lower than any concentration known to cause health effects, either acute
or chronic. Thus, they should provide for a safe work place. In some cases,
chemicals must be separated in the plant in order to obtain pure materials. Here
22
we look at a method of obtaining very pure chemicals by freezing. If a toxic
material can be removed from solution by freezing, not only will the water (in this
case) in which it is dissolved contain less of the chemical, but the chemical that is
frozen will be very pure until the eutectic point is reached.
The van Laar constants for estimating the activity coefficients are
Background: Liquids do not burn in the liquid phase. Rather, when a liquid pool
is ignited, the burning occurs in the vapor just above the liquid surface. In order
for ignition to occur, the fuel concentration in the vapor phase must be higher
than the lower flammable limit (LFL). The LFL is defined as the lowest
concentration of vapor (or gas) in air that can be ignited. The LFL is normally
measured at ambient conditions, about 25 /C and 1.0 atm, and will change as the
temperature and pressure change. However, the rate of change is not large for
small changes in temperature and pressure, and most of the cases of primary
interest are near ambient conditions. The liquid from the free surface of a liquid
pool will evaporate into the atmosphere. If the pool temperature is high enough,
the vapor concentration in the air immediately above the pool surface will reach
the LFL, and a flame will flash across the surface if an ignition source is
provided. The lowest temperature that will result in the flash across the surface is
the flash point of the liquid. The LFL and flash point are related because at the
flash point, the concentration in the air above the pool must be equal to the LFL.
The Upper Flammable Limit (UFL) is the highest concentration of fuel in air that
can be ignited. There is no concept analogous to the flash point for the UFL.
23
chemicals will form flammable vapor mixtures if the liquids are in
a tank open to the atmosphere and the air above the liquid surface
is saturated with vapor. Do you think it would be wise to provide
an inert atmosphere over the surface of these liquids if they are
stored under ambient temperature conditions?
Health and Safety Concept: Acceptable heating value for fuel gas
Background: Most heaters and burners are designed for a specific fuel heating
value, and the heating value must be within a reasonably narrow range for safe
operation of the burner. For example, a gas burner designed for operation on
natural gas could not be fueled with propane without modification because the
heating value of propane is too high, and damage would result. While
modifications can be made to most burner systems relatively easily, to fail to
make the modifications when changing fuel could cause serious safety problems.
24
natural gas exceeds 1050 Btu/SCF, there can be safety problems
with burners because the burners are designed to operate with gas
having a heating value of about 1000 Btu/SCF and a higher heating
value can cause incomplete combustion and abnormally high
temperatures at the burner. Air can be added to the natural gas to
reduce the heating value of the fuel gas. How much air, in SCF,
must be added to 100 SCF of the original fuel gas to reduce its
heating value to 1000 Btu/SCF? What will the composition of the
gas be after air is mixed with it? In the natural gas industry, a
standard cubic foot is measured at 60 /F and 14.7 psia.
Background: All chemical processing plants have storage tanks of some kind.
The tanks may be small and designed to hold only a few gallons of chemical, or
they may be huge, holding millions of gallons of chemical. Most of the tanks
commonly used in the process industries are steel because steel is strong and
relatively inexpensive. It can be used successfully for a broad range of chemicals.
However, steel can rust if it is exposed to the atmosphere under the right
conditions. While the rate at which rusting occurs is difficult to estimate, the
eventual result can be predicted. If the vessel is exposed to a continuous supply
of oxygen, it will eventually rust to the point that there is no steel left. If the
amount of oxygen is limited, the chemical reaction will be limited by the
availability of oxygen or by chemical equilibrium in the oxidation reaction.
2 Fe + 1 O2 ----------> Fe2O3
25
originated. The manufacture of gunpowder is another technology that does not
have a proven origin. We surmise that in both cases the technology was
discovered accidentally, because there was no methodology for the people who
discovered the technology to know what the end product would be worth. While
the end result of either soap manufacture or gunpowder manufacture is the
product of accidental discovery, both have had astounding effects on modern life.
Background: Some chemical reactions are highly exothermic and can produce
very high temperatures. While we usually think of high temperatures being
produced by burning fuels with air or oxygen as the oxidizing agent, there are
reactions that require neither oxygen nor air to be present in the gas phase during
the reaction. The following reaction is an example of one of them.
Al2O3 25 cal/gmole-K
Fe2O3 29 cal/gmole-K
Al 8 cal/gmole-K
Fe 10 cal/gmole-K
26
1996 describes an explosion at the Western Sugar Company in Scottsbluff,
Nebraska. The blast followed a bolt of lightning according to one witness. The
explosion leveled seven of eight silos at the plant and scattered plywood and
sugar up to a mile away ... Its apparent that a dust explosion can cause
substantial damage. In the sugar explosion, one person was still missing and 15
others were injured. The explosion occurred on Saturday when only 31 people
were in the plant. About 150 people normally work there.
27
Safety Problems for a Course in Fluid Mechanics
F-1 An ethylene storage tank in your plant explodes. The distance (R) that the blast wave
travels from the blast site depends upon the energy released in the blast (E), the
density of the air (D), and time (2). Use dimensional analysis to determine:
a) The dimensionless group(s) that can be used to describe the relationship
between the variables in this problem.
b) The ratio of the velocity of the blast wave at a distance of 2000 feet from the
blast site to the velocity at a distance of 500 feet from the site.
c) The pressure difference across the blast wave (P) also depends upon the
blast energy (E), the air density (), and time (2). Use this information to
determine the ratio of the blast pressure at a distance of 500 ft from the blast
site to that at a distance of 2000 ft from the site.
Source Problems
F-3 A toxic oil with a viscosity of 25 cP and SG of 0.78 is contained in a large open tank.
A vertical pipe, made of commercial steel, with a 1 in. ID and a length of 6 ft, is
attached to the bottom of the tank. You find out that the oil is draining through the
pipe at a rate of 30 gpm.
a) How deep should the oil in the tank be for it to drain at this rate?
b) If a globe valve is installed in the pipe, how deep must the oil be to drain at
the same rate, with the valve wide open?
F-4 A storage tank contains ethylene glycol at 1 atm and 20oC (D = 1110 kg/m3 , : =
0.0199 Pa s). The tank is 2 m in diameter and has a horizontal 1 in. (2.54 cm) inside
diameter pipe attached to the side of the tank near the bottom. The liquid level is 3
m above the pipe entrance. If the pipe breaks off right at the tank, what is the initial
flow rate of the ethylene glycol and how long will it take for the ethylene glycol to
drain from the tank?
28
F-5 The pipe connected to the tank in Problem 4 has a gate valve in the line located 3 m
from the tank. If the pipe breaks off downstream of the valve, what will the
maximum flow rate be?
F-6 A storage tank containing ethylene at a pressure of 200 psig and a temperature of
70oF springs a leak. If the hole through which the gas is leaking is 1/2 in. in
diameter, what is the leakage rate of the ethylene, in SCFM?
F-7 A storage tank contains ethylene at 200 psig and 70oF. If a 1 in. line that is 6 ft long
and has a globe valve on the end is attached to the tank, what would be the rate of
leakage of the ethylene (in SCFM) if
a) The valve is fully open?
b) The line breaks off right at the tank?
F-8 The ethylene storage tank in Problem F-7 has a in. diameter horizontal pipe
attached to the tank. If the pipe breaks off at a point 200 ft from the tank, and there
are 4 standard 90o elbows and one globe valve between the tank and the break, what
is the flow rate through the line in SCFM?
F-9 A 2 in. Sch. 40 pipeline is connected to a storage tank containing ethylene at 100
psig and 80o F.
a) If the pipe breaks at a distance of 50 ft from the tank, determine the rate at
which the ethylene will leak out of the pipe (in lbm /s). There is one globe
valve in the line between the tank and the break.
b) If the pipe breaks off right at the tank, what would the leak rate be?
F-10 Oxygen is to be fed to a reactor at a constant rate of 10 lbm/s from a storage tank in
which the pressure is constant at 100 psig and the temperature is 70oF. The pressure
in the reactor fluctuates between 2 and 10 psig, so you want to insert a choke in the
line to maintain the flow rate constant. If the choke is a 2 ft length of tubing, what
should the diameter of the tubing be?
Reaction Forces
F-11 Water at 68oF is flowing through a 45o pipe bend at a rate of 2000 gpm. The inlet to
the bend is 3 in. ID and the outlet is 4 in. ID The pressure at the inlet is 100 psig
and the pressure drop in the bend is equal to half of what it would be in a 3 in. 90o
elbow. Calculate the net force (magnitude and direction) that the water exerts on the
pipe bend.
F-12 A high pressure gas cylinder contains nitrogen at a pressure (P1) of 2500 psig at 60oF.
A valve with a in. inlet and outlet is attached to the top of the cylinder, and a
horizontal in. tubing line is attached to the valve outlet. With the valve open, the
tube breaks off at the valve exit and the nitrogen escapes. Determine the net force
that is exerted on the valve. The loss coefficient for the valve can be assumed to be
0.6.
29
F-13 Figure F-13 illustrates the flow in the nozzle of a relief
valve attached to a large pressure vessel. The fluid is
water at 150oF, and in both cases the pressure in the
vessel is P1 = 100 psig and P2 is atmospheric when the
valve opens. In case A, the fluid impacts on the disk
and is diverted parallel to the disk (90o from the axis of
the nozzle), and in case B the fluid leaves the disk at an
angle of 45o downward from the plane of the disk. The
diameter of the nozzle is 2 inches and the clearance
between the end of the nozzle and the disk is inch in Fig. F-13
both cases. If the loss coefficient for the valve/disk
system is 0.25 based on the velocity in the nozzle, determine:
a) the flow rate in gpm, and
b) the net force acting on the disk, for both case A and case B. (Gravity forces
can be neglected).
F-14 A relief valve is mounted on the top of a large vessel containing hot water. The inlet
diameter to the valve is 4 in., and the outlet diameter is 6 in. The valve is set to open
when the pressure in the vessel reaches 100 psig, which happens when the water is
at 200o F. The liquid flows through the open valve and exits to the atmosphere on
the side of the valve, 90o from the entering direction. The loss coefficient for the
valve has a value of 5, based on the exit velocity from the valve.
a) Determine the net force (magnitude and direction) acting on the valve.
b) You want to attach a cable to the valve to brace it such that the tensile force
in the cable balances the net force on the valve. Show exactly where you
would attach the cable at both ends.
F-15. An emergency relief valve is installed on a reactor, as illustrated in the Figure, F-15,
to relieve excess pressure in case of a runaway reaction. The lines upstream and
downstream of the valve are 6 in. sch 40 pipe. The valve is designed to open when
the tank pressure reaches 100 psig, and the vent exhausts to the atmosphere at 90o to
the direction entering the valve. The fluid can be assumed to be incompressible, with
an SG of 0.95, a viscosity of 3.5 cP, and a specific heat of 0.5 BTU/lbm oF.
If the sum of the loss coefficients for the valve
and the vent line is 6.5, determine:
a) The mass flow rate of the fluid through
the valve in lbm/s and the value of the
Reynolds number in the pipe when the
valve opens, and;
b) The rise in temperature of the fluid from
the tank to the vent exit, if the heat
transferred through the walls of the system
is negligible, and;
c) The force exerted on the valve supports by
the fluid flowing through the system. If
you could install only one support cable to
balance this force, show where you would Fig. F-15
put it.
30
F-16 A relief valve is installed on a pressure vessel as shown in Fig. F-15. The entrance
to the valve is 4.5 in. diameter and the exit (which discharges to the atmosphere in
the horizontal direction, 90o from the entrance) is 5 in. diameter. The loss coefficient
for the valve is 4.5 based on the velocity at the valve inlet. The fluid in the tank is a
liquid, with a density of 0.8 g/cc.. If the valve opens when the pressure at the valve
reaches 100 psig, determine:
a) The mass flow rate through the valve, in (lbm/s), and;
b) The net force (magnitude and direction) exerted on the valve.
c) Determine the location (orientation) of a cable which is to be attached to the
valve to balance this force (note that a cable can only support a tensile force).
31
Safety Problems for a Course in Kinetics
4 135
8 66
12 33
16 16
20 8
24 4
2
Haddad, L.M. and Winchester, J.F., Clinical Management of Poisoning and Drug Overdose, W.B.
Sanders Company, Philadelphia, 1983, pp. 562-575.
32
a) Prepare a nomogram by plotting the above data on semi-log graph paper.
Label the "No Risk" region and the "Possible Risk" region.
d) Data are missing for plasma levels at time equal 0. Explain why or why not
a valid measurement can be made at time equal 0.
Health and Safety Concept: Temperature Control & Stability, Runaway Reactions
Background: Many chemical industrial losses are due to "runaway" reactions and
the associated rapid increase in temperature. This problem helps the student grasp
the influence of temperature on a reaction. They gain an appreciation of the
expression "The reaction rate doubles for every 10C increase in temperature."
k=Ae-Ea/RT
Where:
A is the frequency or pre-exponential factor
Ea is the activation energy for the reaction in interest, J/mol
T is the absolute temperature, K
R is the gas constant 8.314 J/mol K
and the rate of reaction is equal to k(T)*f (conc. of the species
present)
a) A common cited "rule" of thumb is that the rate of reaction k doubles for
every 10C. What activation energy Ea does this correspond to at 50C,
100C, 200C, and 500C respectively?
b) Another "rule" of thumb cites that a "catalyst" lowers the activation energy
for a catalyzed reaction compared to a non-catalyzed reaction by a factor of
2 to 4. If the activation energy found at 500C is decreased by a factor of 4,
what is the incremental increase in temperature needed to double the rate of
reaction?
33
c) Your kinetics text book has values for activation energy for example
reactions. Compare one of these examples to the values found in parts a &
b. What do you conclude?
Health and Safety Concept: Explosion and flammability test units. Autoignition
temperature.
Background: Lower and upper flammability limits of mixtures of fuels and air are
determined in fixed volume vessels. Another flammability property of combustibles
is the auto-ignition temperature - the lowest temperature in which a stoichiometric
mixture of fuel and air will automatically combust without an outside source of
energy (a spark). This problem presents sample experimental information which
might result from an auto-ignition experiment with methane and air. Students are
required to use some of their thermodynamics background (no calculations are
involved). The pressure increases because of temperature not because of a change
in the number of moles. Some students may confuse the problem with combustion
inside a compressed piston chamber.
34
Health and Safety Concept: Corrosion and models to describe
dy/dt = c1 (1)
Where:
y is the thickness of the oxide layer
t is the time
c1 is a constant with units of L/2
Another model is the parabolic growth rate law which models rate of growth
of an oxide film limited by ionic diffusion of O-2 through an oxide layer.
a) Solve both of these differential equations subject to y=y0 at the time equal 0.
0.0 100
0.5 158
1.0 198
1.5 235
2.0 263
2.5 293
3.0 314
3.5 340
4.0 361
35
c) (Graduate Level) Show the derivation of Eqn. 2 starting with Fick's lst law
of diffusion.
Merck Index
a) Write the stoichiometric reaction equation. Assume that the reaction is first
order in ethylene oxide concentration and that it is nearly irreversible. The
first order rate constant is 0.3 min-1.
b) Why can the assumption be made that the reaction is first order in ethylene
oxide concentration only?
d) The technician reports to you that the pilot plant has run out of 1 M solution
of ethylene oxide and that a batch needs to be made up. What important
precaution(s) must be taken in handling ethylene oxide? (Hint: Find an
MSDS sheet on ethylene oxide. What is it's normal boiling point?)
K-6. Dust Explosion Testing
36
Background: Dust explosions can be extremely violent and damaging. For
example, common household cornstarch can explode with energy equal to the release
of energy by an explosion created in a similar amount of methane-air mixture.
Deflagration venting is required to keep losses to a minimum. The nature of a dust
explosion is evaluated in a fixed volume sphere in which a deflagration index is
determined based pressure/time date after an explosion is set. Depending on the
value of Kst the dust is classified into one of three classes (St-1, St-2, or St-3). Dust
Explosion Testing
Dust explosion testing is completed in a fixed volume sphere of about 20 liters
in volume. Approximately 1 gram/liter of dust is dispersed with air into the sphere
for about 3 seconds followed by the discharge of a spark. In the right conditions, an
explosion occurs.
Consider a test on corn starch purchased from a local grocery store [(C6H10O5)]n
a) Write a balanced stoichiometric equation for the combustion of corn starch.
b) If the test vessel is 20 liters and air is added at 1 atmosphere, how many
grams of corn starch is required based on a stoichiometric reaction?
c) The deflagration index is defined as: (see Crowl & Louvar 2002, p.259-260)
dP
K st = V 1/ 3
dT
max
The following data were acquired in a dust explosion apparatus. What is the
deflagration index based on this test?
37
K-7. Sequential Reactions: Halogenation of Benzene to Chlorobenzenes
Health and Safety Concept: Handling and care of benzene and chlorinated
benzenes. Use of MSDS sheets in experimental planning.
a) Review the MSDS sheets on all reactants and products. What major
precautions must be made by operators performing these reactions?
b) If the reactions are conducted at 55C and atmospheric pressure, what are
the phases of each reactant and product?
38
K-8. Production of Acrylonitrile
Level: Undergraduate
This particular problem focuses on only one "node" (the reactor) and asks
students to apply six guide words to process parameters. If this is a group project
the problem can incorporate more of the process, more guide words, and more
process parameters.
Production of Acrylonitrile
Acrylonitrile is an important monomer in the polymer industry, consider the
simplified process flow sheet shown below:
3
Guidelines for Hazard Evaluation Procedures, American Institute of Chemical Engineers, New York,
1985.
39
You are to make up a HAZOP status sheet for the reactor vessel for two process
parameters of temperature and reaction using the five words given above. The
columns can be labeled as:
Health and Safety Concept: Runaway reactors, the necessity of proper relief
valve sizing.
Consider a 2.27 m3 batch reactor charged with 20% vinyl acetate and 80%
acetone by mass. At 60C the desired polymer, polyvinyl acetate, is achieved in
1h with 1 kg of a peroxide based initiator. 90.0% of the vinyl acetate reacts
within this period. The cooling water jacket is designed to handle this heat load
and maintains a constant temperature of 60C.
40
K-10. Identification of Initiation, Propagation, and Termination in an Accident
A vapor cloud explosion (VCE) is the most feared of explosions. Many lives
have been lost and considerable destruction has occurred. Consider the following
events:
At a propane storage tank farm a valve began to leak. A vapor cloud of
propane traveled across a distance of 200 m. The cloud reached an ignition
source at a building located off site. A large fire ball was ignited and flashed
back to the tank farm. Many fires resulted and subsequently many fire balls
called BLEVES occurred. Finally, the fuel is consumed and the fires ceased.
Over 500 lives were lost and $100,000,000 in damage resulted from this accident
(for photographs see SACHE Slide Lecture: Seminar on Tank Failures by Willey,
1993). Crowl and Louvar, 2002, identify that most accidents follow a three step
sequence. In fact the same terminology is used in polymerization reactions;
however, the definitions are different.
d) Estimate the time for the flame front to flash back 200 m back to the tank
farm if the flame speed of propane is approximately 3 m/sec. Actual
flame speeds are extremely dependent on prevalent winds, and obstacles
such as buildings. Flame speeds up to sonic (~300 m/s) or higher are
possible under certain conditions.
41
K-11. Compliance with OSHA List of Hazardous Chemicals
Level: Undergraduate
O
OH OCNHCH3
CH3N=C=O + (2)
-Naphthol Carbaryl
OH O-C-Cl
-Naphthol Chloroformate
O O
O-C-Cl OCNHCH3
42
a) You are the manager of environmental health and safety for a small
chemical company. It has been proposed that the company produce
carbaryl. Which chemicals above are on OSHA's List of Hazardous
Chemicals in OSHA's Process Safety Management Standards 29 CFR
1910.119?
b) Several of these chemicals are extremely toxic. In fact, one chemical was
responsible for many of the civilian casualties that occurred in Bhopal,
India, December 3, 1984. Review the article in "Chemical and
Engineering News, February 11, 1985, p.30 and discuss which method
you would propose to make carbaryl and why.
Level: Undergraduate
Where:
r is the radius from the center of explosion, m
mTNT is the mass equivalent of TNT, in kg.
4
Inspiration for this problem came from a paper by Whitney, M.G.; Barker, D.D. and Spivey, K.H.,
Explosion Accident Consequences Investigation Methodology, 1992 Proceedings of the Process Plant
Safety Symposium, AIChE, New York, Vol. 1, p.206-218.
43
this equation is valid for pressures < 10 kPa
b) Estimate the time length of the explosion if ignition was in the center of a
spherical vapor cloud with propane concentration approximately at its
stoichiometric concentration. Assume that the flame speed is 3 m/s.
K-13. VSP Data and Analysis
VSP (Vent Sizing Package) data are used to determine vent sizes for reactors
which might have a runaway reaction. A runaway reaction is characterized by an
exothermic reaction whose rate increases rapidly because the heat removal is too
low. Consider the results for a VSP experiment conducted on a 38.531%
methanol 61.147% acetic anhydride mixture by weight. Methanol is the excess
reactant.
Temp. vs time
Pressure vs time
ln dp/dt vs -1000/T
ln dT/dt vs -1000/T
44
c) At what time into the run does the reaction begin to "take off"? At what
temperature did this auto-acceleration occur?
d) The heat released per unit mass, q, due to an exothermic reaction runaway
is estimated from VSP data by the following equation:
Where the subscript, S, is the temperature rise at the relief valve set
pressure and (dT/dt)M is the rate of temperature increase at the maximum
over pressure of the valve. A relief valve which opens at 50 psi gauge
and has 20% over pressure (60 psi gauge max) is being sized for a reactor
for the reaction data above. If Cv is 2,100 J/kg K, what is the value of q
for the relief valve design equation given above?
Where:
Determine the area for a relief valve described in part d holding 9500 kg
of reactants based on the data given in the VSP data. Assume that GT =
3000 kg/m2s and that V=15m3.
5
Leung, J.C., "Simplified Vent Sizing," AIChE Journal, 32(10), 1986, p. 1623.
45
VSP Data6
Time, min T,C -1000/T, K-1 dT/dt,C/mi dP/dt,psi/mn P, psia
0 20.02 -3.411 0.402 -1.152 14.26
43.138 39.01 -3.203 0.438 0.137 16.73
57.659 48.49 -3.109 1.002 0.294 18.99
64.169 57.52 -3.024 2.046 0.791 21.90
66.171 62.29 -2.981 2.903 1.370 24.06
67.674 67.26 -2.938 3.943 2.095 26.49
68.574 71.26 -2.904 4.896 2.784 28.48
69.272 75.30 -2.870 6.192 3.784 31.10
69.558 77.30 -2.853 7.005 4.545 32.23
70.258 83.35 -2.805 9.927 7.219 36.41
70.603 87.37 -2.774 12.463 9.890 39.63
70.885 91.41 -2.743 15.395 12.866 42.61
71.452 103.47 -2.655 26.983 26.448 53.52
71.724 112.91 -2.590 42.782 51.906 65.05
71.841 118.60 -2.553 52.095 67.093 71.09
71.888 121.19 -2.536 57.378 80.556 75.19
71.915 122.85 -2.525 60.792 87.907 77.27
71.940 124.50 -2.515 63.722 94.106 79.38
72.007 129.27 -2.485 75.010 136.347 87.51
72.100 137.01 -2.438 95.777 218.927 105.46
72.203 148.13 -2.374 117.48 313.074 131.18
72.313 161.90 -2.299 125.837 439.771 173.72
72.409 173.10 -2.241 97.51 384.490 192.12
72.501 179.66 -2.208 41.622 176.50 246.02
72.664 182.98 -2.192 3.365 31.219 261.05
72.808 183.18 -2.192 2.001 20.38 270.29
75.063 187.69 -2.170 1.729 12.354 300.24
85.229 205.16 -2.091 1.163 9.083 444.48
93.748 197.06 -2.127 -2.666 -16.013 389.31
101.847 176.84 -2.222 -2.243 -11.066 275.64
6
Data provided by G. Boicourt, BASF Corporation, Wyandotte, MI.
46
K-14. Explosions and Runaway Reactors - Heat Transfer Considerations - An
Introduction.
Health and Safety Concept: The importance of temperature control and heat
removal in exothermic reactions.
Background: Taffanel and LeFloch7 first published rate of heat generation and
removal curves as a function temperative in 1913. Students are provided with
five equations for heat generation and removal (four kinetic and heat transfer) and
are asked to analyze what can happen at various instantaneous temperatures.
and the heat removal equation assuming that heat transfer is proportional
to t-tsurroundings:
Where:
T is temperature in K
t is temperature inC
Q is in kW
b) For the heat generation curve 1. If the initial temperature is 70C what
happens to the temperature? If the initial temperature is 95C what
happens?
c) For the heat generation curve 2. If the initial temperature is 70C what
happens? 95C? 108C?
d) Identify the steady state temperatures for each curve and determine if they
are stable or unstable operating points.
7
Taffanel, J. & LeFloch, G., Comptes Rendus Ac. Sc. 1913, 156, 1544. (From Medard, L. Accidental
Explosions Vol. 1: Ellis Horwood, Chichester, West Sussex, PO 19 1EB, England).
47
e) Note that Qgen3 curve is tangent to the Qrem curve at one temperature
implying
Qrem = Qgen3
and
dQrem/dT = dQgen3/dT
Health and Safety Concept: Tubular flow reactors with exothermic reactions.
Possibility of creep deformation.
-) H = 134,600 kJ/kmol
dV = B (d2/4) dz
8
Taffnel, J. and LeFloch, G. Compotes Rendus Ac. Sc. 1913, 156, 1544.
48
Ft = 38 X 10-9 kmol/s
Where:
R is 8.314 kJ/kmol K
T is temperature in K
c) Plot rate vs. distance on an expanded x axis scale (use intervals of about
0.05 micron) at the point where rate "takes off" in part b.
d) If the reactor tube material is constructed from stainless steel 304, what
can happen in case b
K-16. Batch Reactor With An Overcharge of Catalyst
Health and Safety Concept: Runaway reactors. Proper relief system sizing
9
Mueller, K.H., Walters, J.D., J. Am. Chem. Soc. 73, 1458 (1951)
49
examine the consequence of such an action. The question is designed to be
discussed in class because many fundamental engineering issues are involved.
a) If the initiator charge is 10 kg instead of 1 kg, how does this influence the
overall kinetic equations used to model the reactor?
c) As the reaction proceeds the viscosity of the solution thickens, what will
this do to overall heat transfer?
d) Assume that the overall heat transfer is constant, prepare conversion and
temperature curves as a function of time for the case for when 10 kg of
catalyst is charged into the reactor. What can possibly happen?
Health and Safety Concept: Considerations which must be made during the
start up.
50
your answer with some sample calculations for a typical C2H2
hydrogenation reactor used in an ethylene production plant. (In actuality,
an undocumented loss of $6 x 106 of a supported noble metal catalyst
occurred by sintering)
b) Given the above facts and findings, suggest the correct start up procedure
to get this reactor back on line.
K-18. Modeling Differential Scanning Calorimetry
k = A exp (-Ea/RT)
10
Hofelich, T.C. and Thomas, R.C. "The Use/Misuse of the 100 Degree Rule in the Interpretation of
Thermal Hazard Tests," Proceedings of the Inter. Syms. on Runaway Reactions (1989, Cambridge, MA,
CCPS, AIChE, New York, New York).
51
A, min-1 Ea
3.8 x 104 40 kJ/mol
2.2 x 107 60 kJ/mol
1.3 x 1010 80 kJ/mol
5 x 1015 120 kJ/mol
2 x 1021 160 kJ/mol
Reducing the amount of a hazardous material can increase safety and reduce
cost.12 One place where intensification can be applied is switching from large
batch reactors to smaller continuous reactors. Consider the production of
nitroglycerin (NG) made from a mixture of glycerin, nitric and sulfuric acids.
The reaction is:
11
Kletz, T., Plant Design for Safety - A User Friendly Approach, Hemisphere Pub. Co., New York, 1991.
p. 21-28.
12
Ibid.
52
a) What is the TNT equivalent in kg of a reactor holding 1 metric ton of
products? (The equivalent energy of TNT is 4,681 kJ/kg.)
d) What are the major reactor design differences between the batch reactor
and the continuous reactor? What fundamental change improved the rate
for the continuous reactor?
K-20. The Chemical Kinetics of Explosions
a) Write down the elementary steps for the formation of HCl starting with
Cl2 activated by light in a Cl2 + H2 mixture.
Label the chain carriers. Label the initiation step, the propagation step(s)
and the termination step(s).
13
Medard, Louis A., Accidental Explosions Vol.1 Physical and Chemical Properties, 1989, Ellis Horwood
Limited, Chichester, West Sussex, England.
53
mechanism regarding explosions?
k5
Cl"+W 6 end product
Level: Undergraduate
Health and Safety Concept: Safe storage of materials which can self
decompose.
14
Frank-Kamemetskii, D.A. Acta Physicochimica, U.S.S.R., 1939, 10, 365; Zhur.Fiz. Khim., 1939, 13,
738.
15
Medard, L.A., Accidental Explosions, Vol. 1, Ellis Horwood Ltd., Chichester, England, 1989, 48.
54
Frank-Kamenetskii16 developed the following dimensionless parameter which can
estimate if a gas stored in a constant volume container undergoing exothermic
reaction will self heat and thus possibly explode.
Where:
* - dimensionless parameter
Ea - activation energy
)Urxn - heat of reaction at constant volume
r - the equivalent radius of storage volume as a
sphere
A - the Arrhenius equation frequency factor, 1/s
k - the thermal conductivity
To - the constant temperature around the outside of the
storage vessel
M - molar volume
R - universal gas content
If * exceeds 3.32, the material inside the spherical storage container will self heat
and may eventually explode. Thus, for * = 3.32 given a radius one finds a critical
storage temperature or given a storage temperature a critical radius can be found.
This equation can also apply to systems storing liquids or solids.
16
Frank-Kamenetskii, D.A., Acta Physicochimica, U.S.S.R., 1939, 10, 365; Zhur. Fiz. Khim. 1939, 13,
738.
55
would safely allow the fertilizer to be stored based on the above tests?
A simple burning test is actually a complex kinetic problem to analyze. The test
consists of the ignition of one end of a triangular pile of powder compacted
together placed under a low velocity flowing air stream. The time to burn 20 cm
(or not to burn at all) helps characterize the dust combustibility characteristic.
Dust explosions have been known for approximately 200 years17. Six story mill
buildings have been destroyed by dust explosions originating in grain storage
silos. The ignition of just a teaspoon of corn starch always leaves a memorable
impression on the observer of the severity of a dust explosion.
17
Bartknect, W., Dust Explosions, Course, Prevention, Protection, Springer-Vellag, New York, 1989,
pp.1-33.
56
a) Would the presence of an air flow influence the burning rate for:
NaCl?
Cellulose fiber?
Black gun powder?
c) (Graduate level) Estimate the intrinsic rate constant for the condition
shown in Fig. 1.
K-23. Purification of Process Condensate - Carbon Steel Corrosion
Level: Undergraduate
Increasing amounts of iron corrosion products had entered the HPC system via
the water balance feed line1. The corrosion products eventually blocked CO2
flash vessel packing, thus "overboarding" the system with CO2. Madsen analyzed
this situation through a corrosion mechanism. Students are given the mechanism
and asked to examine a rate equation and provide some analysis. They may need
18
Madsen, J., Process Condensate Purification in Ammonia Plants and Related Facilities Safety, Vol. 31,
AIChE, New York, New York, 1991, 227.
57
their undergraduate chemistry book to look up the definitions of pH and
dissociation constants.
a) Show that the following expressions may be derived from the equilibrium
relationships 2 and 3.
Where K2 and K3 are the first and second dissociation constants for the
dissociation of carbonic acid.
58
Level: Undergraduate-advance standing, first year graduate
A hint you may offer (depending on the students' level) the following
approximation:
Where:
T is the temperature at conversion, x
Ti is the initial temperature
Td is the adiabatic temperature reached at full conversion
x is the conversion of the reactant to its decomposition
products
19
E.S. DeHaven, "Using Kinetics to Evaluate Reactivity Hazards," in Loss Prevention, Vol. 12. AIChE,
New York, 1979, 41.
20
E.S. DeHaven, "Using Kinetics to Evaluate Reactivity Hazards," in Loss Prevention, Vol. 12, AIChE,
New York, 1979, 41.
59
(dT/dt)max = A (Td - Tqm) exp (-Ea/RTqm)
Notation:
c Concentration, kmol/m3
t Time, s
k First order rate constant, s-1
A Frequency factor, s-1
Ea Energy of activation, kJ/mol
T Temperature, K
R Gas constant 0.008134 k J/mol K
Tqm Temperature at maximum temperature rise, (dT/dt)max
Td The adiabatic temperature after full decomposition or self
polymerization
(dT/dt)max Maximum rate of temperature rise
Mr. DeHaven then defines the "L system" which is defined base 10 logarithm of
(dT/dt)max and assigned the following NFPA reactivity index.
Td, K Ea A, sec-1
propane 626 264.8 8.175 x 1014
ethylene 1005 157.7 6.49 x 1012
acetylene 2898 168.5 1.55 x 1012
tert-butyl hydroperoxide (919 + 100)21 158.2 1.023 x 1016
21
For peroxides use Td + 100 see D.R. Strull in "Linking Thermodynamics and Kinetics to Predict Real
Chemical Hazards," in Loss Prevention, Vol. 7, AIChE, New York, 1973, 67. Data shown in part b) are
from a table in this paper.
60
Level: Undergraduate - late kinetics course when a different type of problem is
needed.
Detonation - an introduction
a) What is a deflagation in a gas mixture?
Where:
v is the flame speed in m/s
* ratio of the specific heat capacities at constant pressure to constant
volume (cp/cv) ~1.32
)U is the change in internal energy (J/kg)
1. C3H8 + Air
22
Reviewed in Medard, L.E., Accidental Explosions, Vol. 1, Physical and Chemical Properties, Ellis
Horwood Ltd., Chichester, England, 1989.
61
reaction conditions.
Background: Trevor Kletz writes that plants can be made safer by reducing
inventory of hazardous materials, using safer materials instead and using
hazardous materials in a less hazardous form23 . Another chapter discussed ways
of limiting effects of failures by change in reaction conditions. Students are asked
to consider the example Dr. Kletz used to demonstrate "limitation".
Shown below is a batch reactor used to make a co-polymer. If by mistake the first
stage reactants (A and B) were added during the second stage reaction period or
the second stage reactants (C and D) were added during the first stage reaction
period a runaway would occur. Discuss an alternative reactor design which could
avoid or minimize the potential runaways.
23
Kletz, T., Plant Design for Safety - A User Friendly Approach, Hemisphere Publishing Corporation,
New York, 1991, p. 73.
62
K-27. Use and Abuse of Low Temperature Shift Catalyst
a) Explain how and why two separate reactors are used in ammonia synthesis
plants?
CO + H2O + s X I"s
I"s X CO2 + H2 + s
H2O + s X H2 + O " s
CO + s X CO " s
c) What are possible catalyst poisons for the low temperature shift (LTS)
catalyst bed?
24
Kitchen, D., Henson, W.G.S., Madsen, J.K., "Use and Abuse of Low-Temperature Shift Catalyst,"
Ammonia Pant Safety, Vol. 30, AIChE, 1990, 105.
63
be considered for the reduction process?
K-28. Conversion of Stack Gas SO2 to Elemental Sulfur
Background: Brown et. al.25 described and modelled a process to remove SO2
from stack gases using an activated carbon multistage bed. The activated carbon
removes the SO2 in the first stage then it passes through to a sulfur generator
followed by a sulfur stripper followed by a hydrogen sulfide generator. Their
work showed a rate equation which students are asked to examine.
activated
SO2 + 1/2 O2 6 SO3 (sorbed) (1)
carbon
activated
SO3 + H2O 6 H2SO3 (sorbed) (2)
carbon
The activated carbon with H2SO3 was then regenerated through a multibed
process.
a) You are assigned to study the rate of reaction 1) and 2) in flue gas
constituents. What are the major variables which must be studied?
25
Brown, G.N., Torrence, S.L., Repik, A.J. Stryker, J.L., Ball, F.J., "Conversion of Stack Gas SO2 to
Elemental Sulfur by An Activated Carbon Process," in "Recent Advances in Air Pollution Control," R.W.
Coughlin, R.D. Siegel, and C. Rai Eds. AIChE Symposium Series #137, Vol. 70, 1974.
26
Ibid.
64
b) What type of kinetic expression is this?
e)27 Consider an inlet gas steam of 1 m3/h (STP, for a pilot plant) composed of
2,000 ppm SO2, 150 ppm NO, 13% H2O, and 3% O2 at 366 K and an
entering flow of solid of activated carbon which flows countercurrently.
If the inlet xv = 0 and outlet xv = 0.01, how much activated carbon is
required per time and what residence time is required to achieve 95%
conversion of SO2.
1) Dont bother telling anyone, after all it is a job, and you are doing what
you are told.
2) Tell your supervisor, and wait. Supervisor comes back with the
following reply. Its a State job. They wont accept any changes.
3) Tell the purchasing agent. He replies. Its a State job, we bid low and
any way that we can save money is a must
4) Write a letter to the steam plant superintendent with copies to your
supervisor and the purchasing agent after exhausting 2 & 3.
5) Dont tell anyone and quit!
27
Graduate level
65
Safety Problems for a Course in Heat Transfer
Health and Safety Concept: Proper heat exchanger sizing reduces chances of
runaways.
Background: Properties of fluids play an important role in heat transfer and the
resultant exchanger length required to accomplish a given amount of heat transfer.
Occasionally, vessels and heat transfer elements designed for one application
have been proposed to be used for another application without consideration of
viscosity and density changes. The most severe case is a vessel used for an
exothermic reaction of a very viscous medium in which the heat transfer coils are
undersized because they were initially sized for a lower viscosity medium. The
result can be a runaway reaction. This problem compares the properties of
three materials and the influence that properties have on the Reynolds number,
the Prandtl number, and Nusselt number and the resultant heat transfer
coefficient.
Questions:
10 kg/min of water, air, or glycerin need to be heated from 5 to 15C in a 2.5 cm
diameter tube.
Re = 4* m / B d :
Where:
Re = Reynolds Number
m = Mass flow rate
d = Characteristic length (Diameter)
= Viscosity
Pr = L/" = : cp/k
66
Where:
L = Kinematic Viscosity
" = k/cp
: = Viscosity
cp = Heat Capacity
k = Thermal Conductivity
Compare the Reynolds number and Prandtl number of air and glycerin as ratioed
to water for each of these materials flowing at 10 kg/min at Tave through a 2.5 cm
tube.
c) You will learn a number of correlations for heat transfer. A rather simple
one is the Dittus Boelter relation for heating of a fluid when the flow
regime is turbulent. The Nusselt number (Nu) is given as follows:
When the flow regime is laminar and the pipe is extremely long with a constant
wall temperature, the Nusselt number is found to be a constant:
Nu = 3.66
The amount of heat transfer for a pipe is described by Newtons Law of Cooling.
q= h A (Tw-Tave) = h B D L (Tw-Tave)
Where:
Assume that (Tw-Tave) = 50C, compare the Nu, q required, and finally the length
required to heat each fluid from 5C to 15C. What properties influence the
length most for air and glycerin compared to water?
HT-2. Insulation of a Hot Pipe
Health and Safety Concept: Insulating hot pipes eliminates occurrence of burns
67
Background: Many companies define unsafe surface temperatures of hot
objects at TSURFACE > 60C up to a height of 8 above the floor. Burns may result
upon contact of surfaces above 60C. When an outer wall temperature of a pipe is
above this temperature, insulation is required28.
Questions:
a) Given the following wall temperatures, calculate the minimum thickness
of fiberglass insulation required to lower contact temperature to a safe
temperature (60C and below). Use fiberglass insulation with a thermal
conductivity of 0.035 W/m2 C. The pipe is 2-inch Schedule 40. Assume
an ambient temperature of T = 20C, and a convection heat-transfer
coefficient of 3.0 W/m2 C.
Twall = 100C; 200C; 300C; 400C; 500C.
b) Determine the pipe wall temperature for an insulated pipe which has 0.5
inches of fiberglass insulation and an outside surface temperature of 60C.
c) Commercial organically based heat transfer fluids are often used in high
temperature applications. Discuss what can happen if these fluids leak
into the insulation surrounding the pipe. (Reference: Spontaneous
Insulation Fires, Dr. L. Britton, AIChE Loss Prevention Symposium,
1990.)
HT-3. Influence of Thermal Conductivity
Questions:
a) Consider a 2 m diameter tank, which is well insulated resulting in
negligible heat loss, holding 5 m (in height) water. Heat transfer via
28
The author acknowledges the assistance of Mark Bellisario in the formulation of this problem.
68
radiation is providing a constant heat flux to the top of 6 W/m2. At the
bottom of the tank is a heat sink which keeps the bottom of the tank at a
constant temperature of 20C. Estimate the top surface temperature.
b) Repeat part a) for the tank holding 5 m of ethylene glycol.
c) What is the flash point of ethylene glycol, and therefore, what is its
classification?
d) In consideration of the answers in part a), b) and c), what are some of the
concerns one might have about subjecting the ethylene glycol to this type
of heat flux?
HT-4. Determination of the Evaporation Rate of Liquid Nitrogen from a Cryogenic
Container
Background: Liquid nitrogen is stored in cryogenic tanks that are well insulated
to prevent boil off. The question below is used to estimate the relief valve size
required because of heat transfer by conduction through the insulated jacket29.
Questions:
a) Determine the inside diameter of the following cryogenic storage tank.
The total volume of the cylindrical tank for liquid is 240 liters and an
inner height of 1 meter. The wall of the tank consists of three layers of
material. The inner and outer layer of the wall is 1.5 mm 304 stainless
steel. The central layer of the wall consists of an evacuated space with
insulation at a thickness of 22 mm.
b) Determine the heat flow through the wall of the tank and the evaporation
rate. Assume the liquid nitrogen is stored at 23 psig and -188C and that
the ambient temperature is 24C. The thermal conductivity of 304
stainless steel and the insulation can be assumed constant at values of 120
W/mC and 0.72 mW/mC, respectively. The latent heat of vaporization
of nitrogen is 5.577 kJ/gmol. Neglect the heat transferred through the
ends of the cylindrical tank, convection, and radiation effects.
c) Consider that over a period of time, the evacuated space in tank wall filled
with air at atmospheric pressure. Determine the heat flow (W) through the
wall and the evaporation rate (kg/h) under these new conditions. Assume
that the thermal conductivity of the layer of insulation with air will be
equal to the thermal conductivity of air.
d) Determine the diameter required for a relief valve to properly fit the tank
using the following equation30. Size the relief valve using the maximum
possible evaporation rate of the liquid nitrogen. Assume a discharge
29
The author acknowledges the assistance of William Menaker in the formulation of this problem.
30
Crowl, D. A. & Louvar, J. F. Chemical Process Safety: Fundamentals with Applications. 2nd ed.
Prentice Hall, Englewood Cliffs, New Jersey, 2002, p 390. Eqn. 9-6.
69
coefficient of 1.0 and the ratio of heat capacities of 1.4.
( +1 ) /( 1 )
Q T g 2
A= m c
CoP M R c +1
Where:
A = area of discharge
Qm = evaporation rate
Co = discharge coefficient
P = absolute upstream pressure
= ratio of heat capacities
gc = gravitational constant
M = molecular weight
Rc = ideal gas constant
T = absolute temperature of discharge
HT-5. Determination of Evaporation Rate of Propane
31
The author acknowledges the assistance of William Menaker and Professor Reed Welker in the
formulation of this problem
70
are now required by Federal rules and the tank cars must be insulated to keep the
walls in the vapor space cooler during fire exposure.
Question:
LPG is stored in a cylindrical carbon steel tank with hemispherical ends and is
equipped with a relief valve that opens at 260 psig (a boiling temperature of about
T=54C). The tank is 10 m long and 3 m in diameter and is initially at 90 % full.
Heat from an impinging flame is transferred to the wall surface by two
mechanisms: radiation and convection. Then, heat is transfer though the tank
wall to the boiling liquid by conduction. Assume that a flame (T=1,100C) is
striking an area of 20 m2 along the tank wall up to a point 1 m high on the side.
For radiational heat transfer, use a view factor of 0.3 and an emissivity function of
1.0 (really absorptivity in this case). For convective heat transfer, use a
convective heat-transfer coefficient of 20 W/m2 C. For conductive heat transfer
through the wall assume that the tank wall has a thickness is and a thermal
conductivity of 43 W/mC. Estimate how long it takes for LPG to boil off from
90% full to a height of 1 m assuming that the liquid inside the tank is at its
constant boiling temperature of 54C. The time is approximately the time
available for firemen to put out the flame and evacuate the surrounding area
before a BLEVE occurs. Use a heat of vaporization for LPG at 380.6 kJ/kg and
the liquid density at 532 kg/m3.
HT-6. Determination of the Temperature at the Tip of a Fin
Background: Hot surfaces can burn human skin. A rule of thumb is that any
surface above 140F (60C) can cause a burn on a person. Consider the following
finned tube heater that might be considered for use in a home32.
Questions:
A house is heated with forced steam through a longitudinal fin-tube heat
exchanger. Saturated steam is at pressure of 25 psia and is forced through a 50 ft
copper pipe (OD = 1 inch, ID = 0.8 inch). There are a total of 8 aluminum fins
with a longitudinal length of 50 feet, a height from the base of the pipe of 2
inches, and a thickness of 1/16 inch. The ambient temperature is 70F and the
mass of condensate measures at 100 lb/hr. Assume that all heat transferred
through the copper pipe wall is transferred through the fins only.
a) Find the heat flow through the copper pipe wall.
b) Calculate the outside wall temperature of the copper pipe.
c) Calculate the heat transfer coefficient, h, from the aluminum fin to the air.
d) Find the temperature at the tip of each fin.
e) Is the tip temperature safe for children to come into contact with? If the
32
The author acknowledges the assistance of William Menaker in the formulation of this problem
71
answer is no, what could be done to prevent contact by children?
HT-7. A Pipe Too Long
Background: Plumbers often use rags which accumulate oil and hydrocarbons
over time. On rare occasions, these rags are left on a floor near a furnace or a
72
heat source. Over time these rags can begin to heat because of heat transfer by
radiation and convection. If the material in the rags is combustible, the
temperature could reach the auto-ignition temperature and the rags will then catch
on fire. For more general article on the prevention of fires for thermal fluid
systems, see J. Oetingers article in CEP, Vol 98 (1), pp 46-48, 2002.
Questions:
a) Determine the auto-ignition temperature for hexane33.
b) An incinerator used in the combustion of trash and for the production of
steam has an internal wall temperature of 301C and an external wall
temperature of 300C. The walls are carbon steel and 1/2 in thickness.
The incinerator dimensions are 10 wide, 20 long, and 12 high.
Estimate the total amount of heat lost through the walls.
c) A workman leaves a pile of rags soaked in a high boiling point oil with an
auto-ignition temperature similar to hexane (approximately 1 kg of oil and
rags in a spherical shape with a diameter of 8 and with an initial
temperature of 20C) 12 away from the wall of the furnace. Let the
effective thermal conductivity of the air between the rags and the furnace
be 0.05 W/m C. The effective heat capacity of the rags is 2,400 J/kg C.
Using the maximum heat flux to the rags from the furnace wall and
assuming no evaporation, estimate the time that the janitors have before
these rags may self ignite.
HT-9. Cooling of a French Fry
Health and Safety Concept: Allowing hot food to cool off prevents mouth
injuries in the food industry.
33
This is a property of the material and is usually available on MSDS sheets or within an index like the
Merck Index
34
The author acknowledges the assistance of Mark Bellisario in the formulation of this problem
73
french fry has properties of water.
HT-10 Determination of the Cooling Time for a Potato Puff
35
The author acknowledges the assistance of William Menaker in the formulation of this problem
74
mass transfer. Simplified equations are (assuming steady state cooking)36:
Temperature of the oil bath as a function of position:
v MTo/Mx = -(htao/cpoo)*(To-Tc)-(alDhfg/cporo)*Nm
v MTc/Mx = +(htac/cpcc)*(To-Tc)
Notation:
ac interfacial surface area passing a point per unit time of the chip
divided by the volumetric flow rate of the chips, m-1 s-1.
al 1/(volume element of oil) in which evaporation is occurring, m-3.
ao interfacial surface area passing a point per unit time of the chip
divided by the volumetric flow rate of the oil, m-1 s-1.
cpc heat capacity of the chips, J/kg s.
cpo heat capacity of the oil, J/kg s.
ht heat transfer coefficient., W/m2 C.
hfg heat of vaporization of water, J/kg.
D diameter of the chip, cm
M mass fraction of water in the chip, dimensionless 0<M<=1.0.
Nm rate of evaporation within a volume element, al, kg/s
Tc lumped temperature of the chip, C
To temperature of the oil, C as it enters the fryer.
t time, s.
v velocity of the material through the fryer, m/s
x the linear position down the fryer, m.
c density of the chips, kg/m3.
o density of the oil, kg/m3.
Assuming that the fryer is 1 m wide, 18 meter long and an oil depth of 0.1
meter, determine and plot oil and chip temperatures as function of position
within the fryer for an oil feed rate of 0.3, 0.6, and 1.2 m3/min and a potato
feed rate of 200, 400, and 800 kg/hr. The oil enters at a temperature of
175C and the sliced potatoes enter at a temperature of 25C. The oil has
a density of 805 kg/m3 and a cp of 2,483 J/kg C. Assume that the potatoes
have properties similar to water. Use a heat transfer coefficient of 10
W/m2 C.
b) HAZOPS (Hazardous and Operability Study) is one of several methods to
analyze a process for hazards. The overall process is usually done in
36
These equations are simplification of equations presented by Feng, W., Shouche, S., and Nikolaou, M.
Modeling and Predictive Control of a Continuous Fryer, Poster Session, AIChE Annual Meeting Nov
12-17, Miami Beach, Florida, 1995.
75
teams; however, to demonstrate the method consider the following. The
HAZOPS method is applied to process vessels and lines (nodes). Using
guide words of no/not/none, more/higher/greater, less/lower, other
than, and sooner/faster process parameters such as temperature and
reaction can be evaluated as to what is the possible cause and possible
consequence. For example examination of temperature higher within
the fryer may be caused by the oil heat exchanger operating at too high of
a temperature. Possible consequences might be burnt chips. Installing a
temperature controller on the heat exchanger would reduce the likely hood
of over heating the chips.
You are to make up a HAZOPS status sheet for the fryer using the process
parameters of entering oil temperature and oil flow rate using the five
words above. The columns can be labeled as:
Questions: You are an engineer specifying a cooling plate for thick shakes.
Shakes are prepared at 82C, and it is proposed to pre-cool to 78 C by passing
the material across a 0.1 m wide flat plate with a surface temperature of 4C.
Mass flow rate is estimated at 0.1 kg/s and fluid thickness is 1 cm high.
76
HT-13 Tricky Flame Arresters
Health and Safety Concept: Flame arresters are important process safety
equipment
Background: Flame arresters are installed in many process lines and within
vents for large hydrocarbon storage tanks. One type of an arrester is a thin wall
metal arrester composed of a crimp metal between two metals forming a
corrugation similar to corrugated cardboard. This corrugated sheet is then rolled
up to form the core of the flame arrester. An excellent review is available in Ref
137.
Questions:
a) A flame velocity within a pipe can vary tremendously from a deflagration
(a reaction or flame front moving at a speed below the speed of sound) to
a detonation (a reaction or flame front moving faster than the speed of
sound). Consider a flame front approaching a triangular cell shaped flame
arrester as drawn in Figure 1 at the speed of 100 m/s (a deflagration) and a
temperature of 1,100C. Someone suggested that this device quenches the
flame by lowering the gas temperature below the autoignition point of the
gases (say 300C in this problem). If the average wall temperature of the
metal is 200C during the quenching process, how long does the flame
arrester have to be? Assume the properties of air for the combustion gas
mixture.
b) The actual quench mechanism is related to the combustion reaction.
Review your chemistry textbook under elementary combustion reactions
and supply an answer as to what is the flame arresters real quench
mechanism.
60o 0.017
Metal thickness 0.002
37
Howard, W. B. Flame Arresters and Flashback Preventers, Plant Operation Progress, Vol 1, No 4, p
203, Oct 1982.
77
HT-14 When Can You Put That Iron Away?
Background: Hot surfaces can burn human skin or cause fires. A rule of
thumb is that any surface above 60C can be unsafe. Consider the following
simple everyday example below38.
Question:
Your first job interview is about to occur and you have decided to iron some
clothes the night before. You pull out an iron which has a stainless steel
polished plate to serve as the ironing surface. When sitting vertical, the surface
can be roughly modeled as a vertical rectangular plate of 4 wide and 8 high.
After you have ironed your clothes you now desire to put the iron away. The
surface temperature at the time of unplugging is 110C and the iron is left in the
vertical position. How long should you wait before you put the iron into the
closet? Your room temperature is 20C.
HT-15 How Hot Is That Electric Fry Pan ?
Background: Hot surfaces can burn human skin. A rule of thumb is that any
surface above 60C can burn a persons finger when touched.
Questions:
a) Its Thanksgiving morning and you are home for the holidays. Your
mother pulls out a 1350 W electric fry pan and begins to cook pancakes.
You have just had a lecture on free convection from horizontal surfaces,
and therefore; offer to estimate the pans real surface temperature. If 5%
of the rated energy leaves the 10 by 10 top surface by free convection,
estimate the surface temperature of the electric fry pan. The surrounding
air temperature may be taken as 20C.
b) The pan has an edge that is 1 high and 1/8 thick. The surface
temperature is set at 204.4C (400F). Using a film temperature of
112C, estimate the film coefficient for heat transfer from the vertical
edge.
c) Is it safe to touch the top edge? Estimate the temperature at the upper
edge by treating the edge like a fin. Assume that the pan is made of
aluminum.
38
The author acknowledges Ms. Michelle Hoey for the suggestion of this problem
78
HT-16 Snow in July
Adapted by John Fuller40 from Rachel Carson The Silent Spring, Fawcett
Publications, Inc. Greenwich, Conn., 1962
On Saturday, July 10, 1976, this prophecy was filled. A community did suffer all
of the misfortunes Rachel Carson wrote about in Chapter 1 in her 1962 book the
Silent Spring. This community was Seveso, Italy.
The story begins with a reactor vessel 2.3 m in diameter and 3.4 m high
where 2,3,5-trichlorophenol(TCP) was being synthesized from 1,2,4,5-
tetrachlorobenzene in NaOH, ethylene glycol, and xylene. Heating was done by
coils surrounding the vessel using superheated, 12 bar, steam (saturation
temperature of about 188C) as the heating medium. Most of the processing was
done at 170C. On the day of the accident, as the reaction step finished, the crew
decided to leave for the weekend before finishing the final processing step- the
addition of quench water. Six hours later the reactor system over pressurized and
a release of NaTCP, NaOH, and approximately 2 kg of 2,3,7,8
tetrachlorodibenzopara-dioxin (an extreme toxin) left the reactor. The relief
system worked exactly as designed by preventing the explosion of the reactor;
however, the relief went directly into the environment above roof. It was then
dispersed by a wind across the country side where children playfully thought it
was snowing. Eventually, this snow, which did not melt, altered the life style
of several hundred of Seveso residents forcing them to give up their homes and
move to another location and overall altered the way chemicals are processed in
Europe via the initiation of a European directive on the handling of toxic
39
A set of slides about this accident are available as a SACHE product. See Seminar on Seveso Release
Accident Case History, prepared by Ronald J. Willey, AIChE 1994.
40
Fuller, John G. The Poison that Fell from the Sky, Random House, Inc. New York, 1977.
79
chemicals.
In search of the cause of the accident, examination of heat transfer played
an important role. An auto initiation temperature of 220C (a temperature
where the materials could self-react exothermally creating other products) was
known. However, the reactor was left at 170C when it was shut down. So how
did it heat? The answer was in the superheated steam. Its entering temperature
was 300C. Heat transfer to the upper surface of the liquid occurred by both
conduction/convection and radiation. This problem takes a simplified look at
both heat transfer mechanisms.
Questions:
a) Compare the ratio of enthalpy available in steam as it cools from 300C to
its saturation temperature with the amount of enthalpy available as the
steam condenses. What conclusion might one make here?
b) The reactor vessel was only 1/3 full. Thus, the upper walls of the reactor
vessel were near 300C when the reactor was shutdown. If the reactor
walls were 300C at a location of 0.1 m above the rim of the liquid/wall
interface and the wall temperature at the rim was near 170C, estimate the
heat flow inside the wall by conduction through the stainless steel from
the 0.1 m location above the rim to the rim. Assume that the reactor
vessel was made of stainless steel and had a thickness of 1.25 cm.(Ans.
1914 W)
c) Next assume that the temperature at the rim interface was 300C and that
the bulk fluid temperature was 170C. Estimate the required film
coefficient for all of the heat flow from part b) to travel from the reactor
wall into the reactor fluid within the first 1 cm of liquid height below the
surface. What is the temperature rise per hour for the liquid (cp=2740 J/kg
C, density =1050 kg/m3) for this liquid volume under these conditions?
Based on the magnitude of the heat transfer coefficient and the rate of
temperature rise does heat transfer by conduction explain the rise in
temperature beyond 220C in six hours?
d) Another explanation for localized heating was heat transfer by radiation
from upper reactor walls to the fluid surface. If the radiation shape factor
from the liquid surface (at 170C) to the upper reactor walls (at 300C)
was 0.2 and the emissivities of the wall and the liquid were 0.8 and 0.9
respectively, estimate the rate of heat transfer by radiation to the surface
of the liquid. Determine the heating rate,C/hr, assuming that the rate of
energy accumulated is equal to the energy received at the surface by
radiation and that only the first cm of liquid is heated by this energy input.
Is this also a possible explanation for the temperature rise that occurred
after the reactor was shut down?
e) The experience of others is often the best wisdom. What would you do
differently related to the release system for this reactor?
HT-17 Liquid Nitrogen Spills
80
Health and Safety Concept: Minimum oxygen content in environments must
exceed 18%
Background: Spills of cryogenics, liquid nitrogen and natural gas, show some
veryinteresting phenomena.41,42 Initially, the liquid never wets the surface
because of the Leidenfrost phenomenon, a thin film of gas exists between the
liquid and the surface. Because of this film of gas, little flow resistance is
observed and the material spread quickly and moves rapidly to the lowest point
in the room (often to sewer trenches). During this period heat transfer is entirely
by radiation from the room to the exposed upper surface area of the cryogenic.
Gradually, the surface underneath the cryogenic cools and wetting takes place.
The evaporation rate is then accelerated several orders of magnitude. Secondly,
if the oxygen concentration falls below 19.5% in an environment, people can
faint. Concentrations below 13% can be deadly. An equation, often used for
sweep through purging estimations, can also be used to estimate the time
available to evacuate a room or area when a spill occurs43.
Where:
Q: is flow rate of entering species at concentration C0,
V: is the volume of the room or vessel being purged
C1: is the initial concentration of species in the area, any consistent set
of concentration units can be used
C2: is the final concentration of species
C0: is concentration of species in the entering stream.
t is the time to reach C2.
Questions:
a) A liquid nitrogen tank fails inside a room. The nitrogen forms a pool with
an exposed surface area of 5.0 m2. Calculate the rate of evaporation
assuming radiation heating dominates. The surrounding room conditions
are at a temperature of 25C and at atmospheric pressure. Use a )HvapN2 =
5.577 kJ/mol, and an =0.8.
b) Using a 20 m by 25 m by 7 m room, how long would it take for oxygen
levels to drop by 20%, assuming that no make up air enters the room and
that there is a constant evaporation rate due to radiation heating from the
surrounding room?
c) Once the temperature difference between the contact floor and pool of
nitrogen drops to a certain value nucleate boiling will dominate.
41
This can be seen in an easy classroom demonstration. Pour a small amount of liquid nitrogen into a
control volume. Initially, the nitrogen will dance around (film boiling) with the slightest movement.
Later as the surface cools, N2 evaporates much more quickly, and the class will hear a sizzling indicating
the transition to nucleate boiling.
42
The author acknowledges the assistance of Richard Hennessy in the formulation of this problem.
43
Crowl, D.A., and Louvar, J.F., Chemical Process Safety: Fundamentals with Applications, 2nd ed.
Prentice Hall Englewood Cliffs, NJ, 2002, p 300.
81
Assuming a surface contact area of 10 m2, and using Figure 9-8 in
Holman44, estimate the evaporation rate of nitrogen for a temperature
difference of 20 C.
d) Repeat part b) for nucleate boiling.
( +1) /( 1)
g M 2
(Qm )choked = CoAPo c
R cT + 1
For this problem let:
Co = 1.00
= 1.32
Po = 0.9 MPa
M is the molecular weight
R is the Universal Gas Constant
A is the cross sectional area of the opening
44
Holman, J.P. , Heat Transfer, 7th edition, McGraw-Hill, New York, 1990, p 523.
45
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p-133, Eqn. 4-50.
82
HT-19 An Ammonia Release
Q 1 (x - ut ) 2
< C >= exp 0.92
0.026x2.55 2 0.10x
Where:
<C> is the concentration in the wind direction
Q is the total release amount in kg
x is the distance directly downwind from the release in m
u is the wind velocity in m/s
t is the time in s
46
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p-190
47
This equation is a simplification of Eqn. 5-38 on p-190 in Crowl and Louvar using the substitution of the
equations given for sigma as a function of x. It is for a ground level release and cannot be used for an
elevated release. Dispersion is quite complex and depends upon the local weather and time of day. See
Section 5-2 Crowl and Louvar for more details.
83
HT-20 Hot Water Heaters Can Go Bust
Background: Home electric hot water heaters are a common device found in
many homes and commercial areas. A typical hot water heater is 30 to 40
gallons and consists of a resistant heater element.
Questions:
a) A 40 gallon electric hot water heater is rated at 10 kW and has a 1/4 by 6
foot long horizontal cylindrical resistant heater element. Estimate the
temperature excess if the resistant heater element is 70% efficient.
Assume that the water supply pressure is 50 psig.
b) If peak heat transfer coefficient in the nucleate boiling regime occurred at
a temperature excess of 90F, estimate the peak energy flux and power
through the heater element.
c) How can a current/power overload be prevented from reaching the heater
element?
d) Hot water heaters are equipped with thermostats and relief valves. If the
thermostat failed unsafe (i.e. the thermostat misreads an actual high
temperature as a low temperature) the temperature within the hot water
heater could reach the boiling point and pressurize. Relief valves are
attached to relieve any excess pressure build up and thus reduce the risk of
an explosion. An equation to estimate the cross sectional area of a relief
valve under 2 phase flow conditions is given below48:
Qm Hv gc
GT = = 0.9
A fg CpTs
Q m o fg
A =
G TVH v
Where:
GT is the mass flux through the relief
Qm is the mass flow rate through the relief valve
A is the area of the relief valve
R correction factor, use 1.0 for this problem
48
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd Edition,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p-397, Eqn. 9-15 and p-412 Eqn. 9-35.
84
Hv is the heat of vaporization
Lfg is the specific volume difference between the vapor and the liquid
phase
Cp the heat capacity of the fluid at constant pressure
Ts the absolute saturation temperature at the relief set pressure
Q is the constant heat input
m0 is the mass in the vessel (assume that the hot water heater is full
with
saturated liquid)
V the volume of the vessel
gc -gravitational constant
If the hot water heater is fitted with a 60 psig relief valve, estimate the relief
valve diameter for a 40 gallon hot water tank for an heat input of 10 kW.
HT-21 Insulation of a Heat Exchanger
Health and Safety Concept: Insulating hot pipes eliminates occurrence of burns
49
The author acknowledges the assistance of Mark Bellisario in the formulation of this problem
85
HT-22 Heat of Dilution
Health and Safety Concept: Acid dilution produces heat and materials of
construction.
Assume that all other properties of the acid solution are similar to water.
Coolant coil: 1/2 BWG 20; kc=34.6 W/m C
b) If the process was adiabatic, what would be the approximate outlet stream
temperature?
c) What material(s) would you recommend that the cooling coil be
constructive of?
50
This is an easy classroom demonstration. With great care, add 5ml of H2SO4 to 5 ml of water held in a
test tube (always add acid to water, never water to acid). Let students touch the test tube surface, they
should feel a very hot surface. As concentrated sulfuric acid can cause severe skin burns, students must be
equipped with chemical splash goggles.
51
The author acknowledges the assistance of Richard Hennessy in the formulation of this problem. The
original suggestion was provided by Mr. David Erickson, Office of Radiation, Michigan State University,
East Lansing, MI.
86
HT-23 HTHTM - HIGH TEMPERATURE HEAT TRANSFER MEDIUMS
52
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p-227.
87
however, dont realize how hazardous the valuable titanium can be. One or two
scrap dealers have lost their scrap yard because of this lack of knowledge53.
Questions:
a) A 2-4 shell (inside diameter of 4 with a baffle pitch of 4 and fb=0.1000)
and tube (48-3/8OD 22 BWG titanium tubes, tube pitch of 0.45 inches)
heat exchanger is being designed as a sea water/fresh water heat
exchanger. Typical flow rate and temperature data has been specified as
follows: 25 gpm of sea water entering at 10C on the tube side, 30 gpm
of fresh water entering on the shell side at 80C and exiting at 40C.
What should the tube length be in the new exchanger to meet this heat
transfer demand?
b) Finely divided titanium burns in air at 700C. Larger pieces ignite at
higher temperatures. Once the ignition is initiated, there is no stopping it.
The TiO2 that is formed dissolves in the molten Ti (T>1660C) and the
surface is even more reactive as more Ti is exposed. Further, exothermic
reactions result when iron is present by the formation of iron/titanium
alloys and by the reduction of iron oxide by titanium to metallic iron and
titanium oxide. Scrap dealers often use oxyacetylene torches to cut open
steel units. Look up (or calculate) the adiabatic flame temperature of a
pure oxygen/ acetylene mixture (oxygen to acetylene at its stoichiometric
ratio for full combustion). Can you foresee any problems using this
method to cut open a titanium/carbon steel heat exchanger?
c) What management systems should be in place to prevent accidents like
this before the exchanger goes to the scrap yard?
53
This problem is base on an article by Pines, B.A., Analysis of Titanium/Carbon Steel Heat Exchanger
Fires, POP Vol 11 No 2 April 1992, p 113.
88
140-5/8 BWG 20 steel tubes on a 13/16 square pitch. The tube side
heats 40 psig water recirculated from the pool from 75 to 83F. The shell
side uses 10 psi steam as the heating agent. Determine the length of the
exchanger required to meet these conditions.
b) Explain the root cause for the power plant boiler tube fail?
c) The steam supply to the heat exchanger is on control system consisting of
a sensor (the outlet temperature of the pool water from the heater), a
controller, and a control element (a air operated control valve). If the
power was interrupted to the controller, how should the control valve fail?
Background: Fluid agitation in an agitated vessel with a coil for heat removal is
an important unit process and provides necessary heat transfer to prevent runaway
reactions. This question compares the rate of heat removal to the rate of heat
generated by an exothermic reaction. McCabe, Smith, and Harriot54 present an
equation to estimate the heat transfer coefficient for a set of helical cooling coils
with a turbine agitator inside a tank. The equation is:
The net heat generated by a zero order reaction can be approximated by the rate
constant (as estimated by the Arrhenius equation) times the heat of formation
times the volume of the reactor:
54
McCabe, W.L., Smith, J .C., and Harriot, P. Unit Operations of Chemical Engineering, 5th ed. McGraw-
Hill, 1993, p-451.
89
Where:
Qgen Is the heat released (or required) by the reaction mixture
Ao pre-exponential constant, units of kmol/s m3 for a zero order
reaction
E Activation energy, kJ/kmol K
-)Hrxn is the Heat of reaction, kJ/kmol
R is the Universal gas constant = 8.314 kJ/kmol K
T is the absolute temperature in K
V is the volume of the reactor
Questions:
a) Plot Q generated as a function of temperature from 20 to 70C for a
reaction with a -)Hrxn of 240,000 kJ/kmol (an exothermic reaction), an
A0 of 4.2 X 107 kmol/s m3, and an E of 80,000 kJ/kmol for a reaction
carried out in a 6 m3 reactor.
b) The vessel is 2 m in diameter and is equipped with an turbine agitator of
0.5 m in diameter. The process fluid has a bulk viscosity of 100 cps, a
viscosity at the coil wall of 150 cps, a density of 950 kg/m3, a heat
capacity of 2400 J/kg C, and a thermal conductivity of 0.26 W/m C .
Plot the outside film coefficient as a function of rpm of the agitator
between 50 to 300 rpms. The cooling coil has a diameter of 3 cm.
c) Assume that the coils inside wall film coefficient is 3,000 W/m2C, and
that the agitator design speed is 100 rpm, what is the over all heat transfer
coefficient base on outside coil area? The wall thickness of the coil is 2
mm and provides negligible resistance to heat transfer.
d) It is desired to run the reaction at 50C. What coil length will meet this
need? Assume that all other conditions are as given in part c) and that 10
gpm cooling water is available at 25C.
e) Plot the rate of heat removal as function of batch temperature for this
cooling coil from 20C to 70C. Assume that the water temperature is
constant within the coil at 25C. Plot on the same chart as that used in
part a).
f) If the temperature of the batch for condition d) was perturbed to 55C
what would happen?
g) Is there another safe temperature to run this reaction at? Explain.
90
initiation temperature. At this temperature the heat released by reaction is not
removed fast enough and the materials continue to heat even faster. A runaway
reaction can result with rapid temperature and pressure rises if the tank is a closed
system.
Questions:
a) McCabe et al.55 give an equation for the film coefficient on the liquid side
of a tank with a material under agitation. Estimate the film coefficient
between the liquid and the wall for a 5 ft high, 5 ft diameter tank equipped
with a 24 agitator operating at a speed of 120 rpm. The tank contains a
fluid with a bulk viscosity of 20,000 cps, a wall viscosity of 30,000 cps, a
specific gravity of 1.26, a heat capacity of 2,400 J/kg/C and a thermal
conductivity of 0.290 W/m C.
b) Where on the jacket should the water enter and exit?
c) The tank is constructed of 1/8 carbon steel and the jacket gap is 1/2.
If 20C cooling water is entering the tank cooling jacket at 5 gpm,
estimate the overall heat transfer coefficient for this system.
d) Figure 9.12 in McCabe56 gives the Power Number as a function of
Reynolds Number of a six blade turbine. Estimate the power that is being
delivered to the fluid.
e) To what temperature will the material reach with this power input?
f) What instrument(s) allows one to estimate auto initiation temperature of
a mixture?
g) What precautions should be made to make sure that the material does not
exceed its auto initiation temperature?
HT-28 Introduction to Heat Transfer in Agitated Vessels
55
McCabe, W.L. , Smith, J.C., and Harriott, P., Unit Operations of Chemical Engineering, 5th Edition,
McGraw-Hill New York, 1993, p-451.
56
Ibid. p-250.
91
Smith, and Harriot57 present an equation to estimate the heat transfer coefficient
for heat transfer to or from a jacket of a baffled tank using a standard turbine
agitator58.
2/ 3 1/ 3 0.24
h jDt Da2n cp
= 0.76*
k k w
Where:
Da is the diameter of the agitator blade
Dt is the diameter of the tank
hj is the heat transfer film coefficient at the jacket surface
inside the tank.
k is the thermal conductivity of the fluid within the reactor
n is the revolutions of the agitator per second
other notation are the standard symbols.
Questions:
a) Consider a tank used to prepare a paste by the enzymatic conversion of
cooked starch. Initially the solution inside the tank has properties very
close to that of water at 25C. The heating medium is saturated steam at
1.0 barg. Assume that the tank is 1.8 m diameter and has a turbine
agitator 0.75 m in diameter rotating at the speed of 30 rpm. Determine the
jacket film coefficient under these conditions. Assume that the jacket wall
temperature is very close to that of steam.
b) Estimate the initial total rate of heat transfer if the liquid level is 1.5 m
inside the tank and estimate the initial rate of temperature rise (C/min) for
the batch. Assume that most of the resistance to heat transfer is within the
jacket film coefficient.
c) As the starch solution heats, it reaches a strike temperature where it
becomes extremely viscous. Assume that the viscosity at the strike
temperature is 50,000 cps. Estimate the heat transfer coefficient at the
jacket wall under this condition.
d) Estimate the rate of heat transfer for the starch cook if the strike
temperature is 73C and estimate the rate of temperature rise (C/min) of
the batch at the conditions given by part c).
e) As the starch continues to cook, the viscosity is reduced. Why?
f) Consider that the agitator is shut off and the steam is left on. What could
happen over a long time?
57
Ibid, p-451.
58
Many correlations exist in the literature for other type of agitators and related equipment. See Perrys
Chemical Engineers Handbook, 6th Edition, p 10-19 for examples.
92
HT-29 Double the Trouble
Questions:
a) A double effect evaporator system is to be fed with 20,000 kg/h of 5%
NaOH solution at a temperature of 80C. The concentrated liquor from
the system is to be 40% NaOH. Saturated steam at 300 kPa absolute is
available and the vacuum on the second effect is set at 20 kPa. The system
is a feed forward type. The overall heat transfer coefficient for the first
effect is 4,000 W/m2C and for the second effect is 6,000 W/m2 C.
Calculate the area required in each effect, the steam requirement, the
capacity, and the economy for this system.
b) You are placed in charge of the double effect evaporator system for the
concentration of NaOH. One morning the waste water superintendent is
calling around the plant and reaches your desk. He has noticed a distinct
increase in pH of the waste water stream before it reaches a pH buffering
system over the past 24 hours. List what might be the cause in your
department?
c) You require a new pump on one of the units. What type of specifications
would you make to insure no shaft leaks?
d) A 1 pipe line develops a hole because of corrosion. Supply pressure
to the line is 30 psig. What is the rate of discharge for a 5% NaOH
solution using the following equation from Crowl and Louvar?59
Q m = AC o 2 g c Pg
Where:
Qm is the rate of discharge, kg/s
A is the area of the hole, m2
59
Crowl, D.A., Louvar, J.F., Chemical Process Safety: Fundamentals with Applications, 2nd ed., Prentice-
Hall 2002 p-117.
93
Co is the discharge coefficient, assume a value of 1.0
D is the density, kg/m3
gc is 1 kg m /N s2
Pg is the pressure in the pipe at the discharge, N/m2
e) If a leak like the one given in part d) did occur, what specific actions
would you do to clean up the spill that developed?
Heat Transfer Principle: Sizing of Exchangers with Change of Phase and Sub-
cooling
Health and Safety Concept: Dealing with Short Life Radioactive Isotopes.
60
This problem was suggested by Ernst Schori, Consultant, RD 1 Box 235, Canaan, NH 03741.
61
The author acknowledges the assistance of Richard Hennessy in the formulation of this problem.
94
Safety Problems for a Course in Process Dynamics and Control
PD-1 A large storage tank is filled manually by an operator. The operator first opens a
valve on a supply line and carefully watches the level on a level indicator until the
tank is filled (a while later). Once the filling is completed, the operator closes the
valve to stop the filling.
Once a year the operator was distracted and the tank overfilled. To prevent this
an alarm was installed on the level gauge to alert the operator to a high level
condition. With the installation of the alarm, the tank now overfilled twice per
year. Can you explain?
PD-2 "Fail safe" is a concept used to specify the position of process instrumentation in
the event of power, air pressure, or other utility failures. For instance, the valve
supplying cooling water to a chemical reactor would fail in the open position
("fail open") in the event of a power failure. This would provide maximum
cooling to the reactor and prevent dangerous high temperatures in the vessel.
Specify the proper fail-safe positions for the valves in the following equipment.
Specify either fail open or fail close:
a) A flammable solvent is heated by steam in a heat exchanger. The valve
controls the flow of steam to the exchanger.
b) A valve controls the flow rate of reactant to a reactor vessel. The reaction
is exothermic.
c) A valve controls the flow rate of reactant to a reactor vessel. The reaction
is endothermic.
d) A valve controls the flow of natural gas to a utility furnace in a power
station.
e) A remotely-operated valve is connected to a drain on a storage tank.
f) A remotely-operated valve is used to fill a tank from a supply line.
g) A valve controls combustion air to a furnace.
h) A valve controls the pressure in a steam header.
PD-3 Interlocks are used to insure that operations in a chemical plant are performed in
the proper sequence. Interlocks can be mechanical or electronic. In many cases
they can be as simple as a lock and key.
PD-4 A process operator is given the following instructions: "Charge 10-lb of catalyst
into batch reactor A at 3 hours into the cycle." Determine at least 15 ways in
which the operator might fail to perform the instructions correctly.
95
PD-5 A storage tank is vented to the atmosphere. If a hole develops in the tank the
liquid level, hL, is given by the following differential equation:
Where:
hL is the liquid level height above the leak,
Co is the constant discharge coefficient = 0.61,
A is the cross-sectional area of the leak,
At is the cross-sectional area of the tank, and
g is the acceleration due to gravity.
PD-6 Surge tanks are used to hold intermediate inventory between process units in a
chemical plant. The motivation is to prevent interruptions or changes in
production in one unit from propagating to the other unit. That is, the second unit
can continue to operate at its normal rate using the stored inventory in the surge
tank until the first unit is brought back into normal operation. Likewise, the first
unit can continue to operate if the second unit is interrupted, with intermediate
product accumulating in the surge tank.
Consider a surge tank used to store an intermediate liquid product between two
process units. Assume that the liquid is pumped out of the surge tank at a
constant rate to the second process:
a) Should the tank be low and flat or tall and skinny? What is your selection
basis for this decision?
b) How would you determine the required volume of the tank? Have you
96
also considered the possibility of overflowing the tank?
c) How would the results of part b change if the liquid were toxic or
flammable?
PD-7 Your family has a gas-operated barbecue unit which everyone enjoys during the
summer. The unit operates from a 20-lb propane tank. The problem with these
units is that it is difficult to determine how much propane remains.
You certainly do not wish to accidently run out of propane during the biggest
holiday weekend of the summer, when all the relatives are visiting! One solution
is to buy a spare tank which you can use when the first runs out. However,
doubling the supply of propane more than doubles the risk of an accident leading
to a fire or explosion. Name at least two other methods to reduce the likelihood
of running out of propane without increasing the supply.
PD-8 For all chemical processes, the instrumentation must be capable of tracking
changes in the process, even when the changes occur quite rapidly. For a
particular process, temperature changes as fast as 10C/minute must be followed.
What time constant thermocouple should you select for this operation?
PD-9 A surge tank is used between two processes. The tank is 10-feet high and 20-feet
in diameter.
a) The liquid level is initially at 5 feet. If the input flow is 200 gpm and the
output flow is 0, how long will it take to overflow?
b) The liquid level is initially at 5 feet. If the input flow is 200 gpm and the
output flow is 199 gpm, how long will it take to overflow?
PD-10 Thermocouples in chemical plants are usually found in sheaths. These sheaths
protect the thermocouple and also allow the thermocouple to be removed and
replaced without shutting down the process. One chemical plant had some
thermocouples which did not have sheaths, although they looked like the sheathed
type. This led to an accidental release of toxic and flammable material. Can you
explain why?
PD-11 Liquid levels in storage tanks are frequently determined by measuring the
pressure at the bottom of the tank. In one such tank the material stored in the tank
was changed and an overflow resulted. Why?
PD-12 The tank shown below has an overflow line to prevent overfilling the tank.
During a routine filling operation, the operator was told to stop filling when liquid
began to overflow into the catch-pot. When this occurred the operator stopped
the input flow and the tank was subsequently sucked in due to vacuum. How did
this occur? This tank (like most storage tanks) is only capable of withstanding a
few inches of water vacuum.
97
PD-13 The two-tank system shown below is operating at steady state. The output
volumetric flow for each tank is given by q = h/R where h is the liquid height and
R is a resistance value.
At time t = 0, 10 ft3 of water are quickly added to the first tank. Determine the
maximum deviation in level (feet) in both tanks from the ultimate steady-state
values and the time at which each maximum occurs. Determine the maximum
quantity of material which can be added quickly to the first tank which does
not result in an overflow of either tank.
Data: A1 = A2 = 10 ft2
R1 = 0.1 ft/CFM
R2 = 0.35 ft/CFM
Tank heights = 10 ft
PD-14 The figure below shows two tanks in series, both with independent level
controllers. This configuration will result in the lower tank inevitably
overflowing. Can you explain why?
98
PD-15 Non-return valves are used to prevent materials from flowing backward in a
process line. The figure below shows two non-return valves installed in a process
line to prevent back-flow of a liquid. The process originally had a single non-
return valve, but the corrosive liquid disabled the valve after only a few months of
operation. To solve the problem two valves were installed as shown. This
modification did not improve the reliability of the system. Why? Can you
suggest a better arrangement?
PD-16 A cover plate on a pump housing is held in place by eight bolts. A pipe fitter is
instructed to repair the pump. The fitter removes all eight bolts only to find the
cover plate stuck on the housing. A screwdriver is appropriated to pry off the
cover. The cover flys off suddenly and toxic liquid sprays throughout the work
area.
Clearly the pump unit should have been isolated, drained and cleaned prior to
repair. There is, however, a better procedure for removing the cover plate. What is
this procedure?
PD-17 Pumps can be shut-in by closing valves on the inlet and outlet sides of the pump.
This can lead to a rapid increase in the temperature of the liquid shut inside the
pump.
PD-18 An operator was told to control the temperature of a reactor at 60C. He set the
set point of the temperature controller at 60. The scale actually indicated 0 - 100
percent of a temperature range of 0 - 200C. This caused a runaway reaction
which over-pressured the vessel. Liquid was discharged and injured the operator.
What was the setpoint temperature the operator actually set?
PD-19 The figure below shows a batch reaction system. A batch of glycerol is placed in
the reactor and circulated through a heat exchanger which acts as both a heater
and a cooler. Initially it is used as a heater and when the temperature reaches
115C, addition of ethylene oxide is started. The reaction is exothermic and the
exchanger is now used as a cooler.
a) If the temperature of the glycerol is below 115C, the ethylene oxide will
not react fast enough. Likewise, if the temperature is above 125C the
99
reaction will proceed dangerously fast. What interlock is present on the
system to insure that the temperature is within the proper range?
b) What alarms are present to indicate a low flow condition in the
recirculating loop?
c) How is the pressure within the reactor monitored?
d) An explosion occurred within this unit while instrument FIA was out of
order. All other instruments were functional. What happened? How
could the process be redesigned to prevent this problem?
PD-20 Pneumatic process equipment operates in the range of 3 to 15 psig. Thus, for
example, a signal of 3 psig might represent 0 psig in the process and 15 psig
might represent 1,200 psig in the process.
PD-21 A light in the control room of a chemical plant indicated whether a valve was
closed or not. In reality it only indicated the status of the signal being sent to the
valve. The valve did not close when it should have and the plant exploded.
Why? How would you prevent this problem?
PD-22 Exothermic chemical reactions are frequently dangerous because of the potential
for a "runaway reaction." Cooling coils are provided in batch reactors to remove
the energy of reaction. In the event of a cooling water failure, the reactor
100
temperature rises, resulting in a higher reaction rate and higher energy generation.
The result is a runaway. During a runaway the temperature can rise very fast,
resulting in dangerous pressures within the reactor and a possible explosion.
Loss of cooling can be detected by measuring the temperature within the
reactor and sounding an alarm. Frequently, by the time the alarm sounds, it is
too late. Design a better instrumentation and alarm configuration to detect
loss of cooling more directly. Draw the instrumentation diagram.
PD-23 A flammable liquid is to be stored in a large storage vessel. Two vessels are
available. One vessel is called a "weak seam roof" tank with the weakest part of
the vessel being the welded seam between the roof and the vertical wall of the
tank. The other vessel is a domed roof tank with the weakest part being the seam
along the bottom of the tank. Which tank is the best choice for storing this
material?
PD-24 Water will flash into vapor almost explosively if heated under certain conditions.
a) What is the ratio in volume between water vapor at 298 K and liquid water
at 298 K?
b) Hot oil is rapidly pumped into a storage tank. Unfortunately, the tank
contains some water which flashes rapidly into vapor and ruptures the
tank. If the tank is 10 m in diameter and 5 m high, how many kg of water
at 298 K are required to produce enough water vapor to pressurize the
tank at 298 K and 8" water gauge pressure, the design pressure of the
storage tank?
PD-25 A storage tank has a diameter of 20 ft and a height of 10 ft. The output
volumetric flow from this tank is given by:
qout = (2 ft2/min) h
Where:
h is the height of liquid in the tank.
At a particular time the tank is at steady state with an input flow of 10
ft3/min.
a) What is the steady state liquid height in the tank?
b) If the input flow is ramped up at the rate of 0.1 ft3/min, how many minutes
will it take for the tank to overflow?
PD-26 A gas detector is used to determine the concentration of flammable gas in a gas
stream. Normally the gas concentration is 1% by volume, well below the alarm
limit of 4% and the lower flammability limit of 5%. If the gas concentration is
above the lower flammability limit it is flammable.
A particular gas detector demonstrates first-order behavior with a time
constant of 5 seconds. At a particular time the gas stream is flowing at 1 m3/sec
through a duct of 1 m2 cross section. If the gas concentration suddenly increases
from 1% to 7% by volume, how many m3 of flammable gas pass the sensor before
the alarm is sounded? Is it possible for a plug of flammable gas to pass the
detector without an alarm ever being sounded?
PD-27 A semi-batch reactor is a batch reactor in which the rate of reaction is controlled
101
by the flow of reactant into the reactor.
Consider a semi-batch reactor with a single input flow of pure reactant. A single,
irreversible, liquid phase reaction converts the reactant to liquid product.
Let
= total mass of material in the reactor,
Integrate the equation, using the initial condition given, to determine the
time at which the reactant mass fraction reaches a level of 0.15. At this
concentration a dangerous situation is encountered. If the temperature is
restored, the high mass fraction will result in a runaway reaction with
possible explosion of the reaction vessel.
PD-29 The system pictured below is used to dilute a concentrated caustic solution. It is
started up with pure water in the mix tank. The following variables are defined:
102
b) Usually the final mix concentration is much less than the concentrated
caustic solution. Simplify the model for conditions which give rise to Cc
>> C. When will this occur?
c) Assuming the conditions of part b), derive a transfer function between the
outlet concentration and the volumetric flow of caustic. What is the time
constant for this system?
d) Use the model developed to consider the effect of various failure modes in
the process. Consider the effect of a failure (or stop) in flow qc, and
separately, qw.
PD-30 Controllers can be used to stabilize processes which are normally unstable.
Consider the unstable process represented by the transfer function
PD-31 A process stream carries a fluid at a normal flow rate of 20 CFM. However, due
to pumping, this flow can vary from 18 to 22 CFM over a period of 1 minute. It
is desired to use a small storage tank to reduce the fluctuations. Determine the
minimum tank area and height required to
Comment on precautions you might consider if the fluid were toxic and/or
flammable.
103
Comment on precautions you might consider to prevent overflow during
abnormal conditions.
PD-32 a) Show that for any pump the maximum liquid discharge velocity is given by
Where:
u is the maximum liquid discharge velocity,
Ws is the pump shaft work,
is the density of the liquid, and
A is the pump outlet discharge area.
104
Safety Problems Requiring a Computer for Solution
Originally Prepared by Daniel Crowl
Michigan Technological University, Houghton, MI
Calculate the discharge rate of a liquid through a 10-mm hole, if the tank head
space is pressurized to 0.1 barg. Assume a 2-m liquid head above the hole.
Consider again CA-1. A stream of liquid discharging from a hole in a tank will
stream out of the tank and impact the ground at some distance away from the
tank. In some cases the liquid stream could shoot over any diking designed to
contain the liquid.
a) If the hole is 3 m above the ground, how far will the stream of liquid shoot
away from the tank?
b) At what point on the tank will the maximum discharge distance occur?
What is this distance?
CA-3 Liquid Discharge through a Piping System
Figure CA-3 shows a transfer system between two tanks. The system is used to
transfer a hazardous liquid. The pipe is commercial steel pipe with an internal
diameter of 100-mm with a total length of 10 m. The piping system contains two
standard, flanged 90 elbows and a standard, full-line gate valve. A 3-kw pump
with an efficiency of 70% assists with the liquid transfer. The maximum fluid
height in the supply tank is 3 m, and the elevation change between the two tanks
is as shown in Figure CA-3.
Figure CA-3
105
CA-4 Gas Discharge through a Hole
a) 0 cm
b) 5 cm
c) 10 cm
d) 15 cm
Data:
Heat of vaporization: 3.33 x 105 J/kg
Volume change on vaporization: 0.048 m3/kg
Heat capacity: 2230 J/kg K
Liquid density: 490 kg/m3
Calculate the gas relief through a relief valve for an uninsulated propane tank
with 5 m2 surface area that is exposed to an external pool fire.
Data:
Surface area 5 m2 = 53.8 ft2
Environment factor F 1.0
106
Latent heat of vaporization hfg 333 kJ/kg (Perry and Green, 1984)
1 Btu/hr 2.93 x 10-4 kJ/s
CA-8 Isenthalpic Flash Fraction
Calculate the flash fraction of liquid propane flashed from 10 barg and 250C to
atmospheric pressure.
Data:
Heat capacity, Cp 2.45 kJ/kg K (average 231-298K)
Ambient temperature, T 298 K (25C)
Normal boiling point, Tb 231K (-42C)
Heat of vaporization, hfg 429 kJ/kg at -42C (Perry and Green,
1984)
Calculate the vaporization rate due to heating from the ground at 10 s after an
instantaneous spill of 1000 m3 of LNG on a concrete dike of 40 m radius.
Data:
Thermal diffusivity of soil, "s 4.16 x l0-7 m2/s
Thermal conductivity of soil, ks 0.92 W/m K
Temperature of liquid pool, T 109 K (-164C)
Temperature of soil, Tg 293 K (20C)
Heat of vaporization of pool, L 498 kJ/kg at -164C (Shaw and
Briscoe, 1978)
Estimate the evaporation rate for a 100 m2 pool of liquid hexane at a temperature
of 298 K.
Data:
M 86
Psat 151 mm Hg
107
Vapor pressure at ambient temp.: 0.652 bar abs
Determine the concentration in ppm 500 m downwind from a 0.1 kg/s ground
release of a gas. The gas has a molecular weight of 30. Assume a temperature of
298 K, a pressure of 1 atm, F stability with a 2 m/s wind speed. The release
occurs in a rural area.
a) The time required after the release for the center of the puff to reach the
plant fence line. Assume a wind speed of 2 m/s.
b) The maximum concentration of the gas reached outside the fence line.
c) Determine the distance the cloud must travel downwind to disperse the
cloud to a maximum concentration of 0.5 ppm. Use the stability
conditions of part b).
d) Determine the width of the cloud, assuming a 0.5 ppm boundary, at a
point 5 km directly downwind on the ground. Use the stability conditions
of part b).
108
* molecular weight
* temperature (K)
* pressure (atm)
* isopleth concentration (ppm)
The spreadsheet should also have cells providing the downwind distance, the total
area of the plume, and the maximum width of the plume, all based on the isopleth
value.
Use the following case for computations, and assume worst case stability
conditions:
Develop a spreadsheet program to draw isopleths for a puff. The isopleths must
be drawn at a user specified time after the release. The spreadsheet should have
specific inputs for:
Release mass: 50 kg
Release height: 0m
109
Molecular weight: 30
Temperature: 298 K
Pressure: 1 atm
Isopleth conc: 1.0 ppm
Weather stability: F
Wind speed: 2 m/s
b) At what time and at what distance downwind does the puff dissipate?
Britter and McQuaid (1988) report on the Burro LNG dispersion tests. Compute
the distance downwind from the following LNG release to obtain a concentration
equal to the lower flammability limit (LFL) of 5% vapor concentration by
volume. Assume ambient conditions of 298 K and 1 atm. The following data are
available:
Using the TNT equivalency model, calculate the distance to 5 psi over-pressure
(equivalent to heavy building damage) of an VCE of 10 short tons of propane.
Data:
Mass: 10 tons = 20,000 lb
Lower heat of combustion (propane)(Ec): 19,929 Btu/lb (46.350 kJ/kg)
Assumed explosion efficiency (0): 0.05
Assumed Ec,TNT: 2,000 Btu/lb
CA-20 TNO and Baker-Strehlow Methods for Vapor Cloud Explosions
(Baker, et. al, 1994) Consider the explosion of a propane/air vapor cloud
confined beneath a storage tank. The tank is supported 1 meter off the ground by
concrete piles. The concentration of vapor in the cloud is assumed to be at
stoichiometric concentrations. Assume a cloud volume of 2094 m3, confined
below the tank, representing the volume underneath the tank. Determine the
over-pressure as a function of distance from the blast using:
a) the TNO multi-energy method
110
b) the Baker - Strehlow method
A 1 m3 vessel at 25C ruptures at a vessel burst pressure of 500 bar abs. The
vessel ruptures into ambient air at a pressure of 1.01 bar and 25C. Determine the
energy of explosion and equivalent mass of TNT using the following methods:
A 6 ft3 sphere containing high pressure air at 77F ruptures at 8000 psia.
Calculate the side-on over-pressure at a distance of 60 ft from the rupture.
Assume an ambient pressure of 1 atm and temperature of 77F.
A 100 kg end of a bullet tank blows off and is rocketed away at an initial velocity
of 25 m/s. If the end is 2-m in diameter, estimate the range for this fragment.
Assume ambient air at 1 atm and 25C.
Calculate the size and duration, and thermal flux at 200 m distance from a
111
BLEVE of an isolated 100,000 kg (200 m3) tank of propane at 20C, 8.2 bar abs
(68F, 120 psia). Atmospheric humidity corresponds to a water partial pressure
of 2810 N/m2 (0.4 psi). Assume a heat of combustion of 46,350 kJ/kg.
Additional Data:
Heat of combustion of the liquid: 43,700 kJ/kg
Heat of vaporization of the liquid: 300 kJ/kg
Boiling point of the liquid: 363 K
Ambient temperature: 298 K
Liquid density: 730 kg/m3
Heat capacity of liquid (constant): 2.5 kJ/kg-K
A 25-mm hole occurs in a large pipeline resulting in a leak of pure methane gas
and a flame. The methane is at a pressure of 100 bar gauge. The leak occurs 2-m
off the ground. Determine the radiant heat flux at a point on the ground 15 m
from the resulting flame. The ambient temperature is 298 K and the humidity is
50% RH.
Additional Data:
Heat capacity ratio, k, for methane: 1.32
112
Heat of combustion for methane: 50,000 kJ/kg
Flame temperature for methane: 2,200 K
Eisenberg (1975) reports the following data on the effect of explosion peak over-
pressures on eardrum rupture in humans:
Determine the likely percentage of fatalities from a 20-min exposure to 400 ppm
of chlorine.
A fixed mass of toxic gas has been released almost instantaneously from a process
unit. The release occurs at night with calm and clear conditions. If the gas obeys
the probit equation for fatalities
Additional data:
Molecular weight of gas: 30
Temperature: 298 K
Pressure: 1 atm
Release height: Ground level
Wind speed: 2 m/s
113
Safety Problems for a Course in Mass Transfer
Background: The MSDS (Material Safety Data Sheet) is available for all
chemicals that you will encounter. The MSDS sheet presents several important
pieces of information such as: Identification: This section contains the name, the
chemical formula, CAS number, and synonyms.
Product and Component Data: This section provides mixture compositions
Physical Data: includes physical property data such as appearance, boiling point,
114
specific gravity, and vapor pressure data at various temperatures (very helpful
when you can not find the data any where else).
Fire and Explosion Hazard Data: provides information about the flash point
(FP), the fire point, the lower flammability limit (LFL) sometimes referred to as
the lower explosion limit, the upper flammability limit (UFL) sometimes referred
to as the upper explosion limit, and the autoignition temperature (AIT).
Reactivity Data: contains details about stability, and incompatibilities involved
with storage and contact with various atmospheres and other materials.
Toxicity and Health Hazard Data: provides information about the lethal dose
(LD50),
the threshold limit value (TLV), and the OSHA permissible exposure limits
(PEL).
Ventilation and Personal Protection: contains information about skin and eye
protection when handling and when working around the chemical.
Special Storage and Handling Protection provides details about how to store
the chemical. Spill, Leak, and Disposal Procedures provides the action to take in
the event of a spill.
Questions:
a) Estimate the diffusion coefficient for the system air/benzene at 25C by
the method of Fuller et al.62 Compare this value to the experimental value
of 9.62 X 10-6 m2/s ref. 63.
b) Obtain a copy of the MSDS sheet for benzene. What is the major
environmental, health, or safety issue with personnel handling benzene?
MT-3 That Rotten Egg Smell
Health and Safety Concept: Threshold Limits Values and LC50 (TLV)
Background: H2S is a common foul odor and can be sensed from leaking gas
lines and other sources. It is perceptible in air in a dilution of 0.002 mg/l
(approximately 2 ppb). H2S is a neurotoxin and after a period of time in its
presence, the smell can no longer be detected. To characterize safe levels of
exposures, threshold limit value-time weighted average - TLV-TWA (ACGIH)
and permissible exposure levels - PELs (OSHA) are used. Further to characterize
lethal situations a value called the LC50, lethal concentration, is used where the
subscript 50 represents 50% of the population will die if exposed. Often LC50 are
for mammals like rats
Questions:
a) Estimate the diffusion coefficient for H2S in stagnant air at 300 K and 1
62
E.N. Fuller, P.D. Schettler, and J.C. Giddings, Ind. Eng. Chem., 58, 19 (1966).
63
C.Y. Lee, and C.R. Wilke, Ind. Eng. Chem., 46, 2381 (1954).
115
atm.
b) What are the TLV-TWA and PEL for H2S.
c) Provide an LC50 (with species identified) for H2S.
116
exposed front face after t = 5, 50, and 500 seconds at x=0 m.
b) Go to your library and obtain the information reported in the either the
Merck Index or Sax about Chlorine. Why is chlorine hazardous?
c) How low of a concentration isnt very harmful? What is the TLV-TWA 8
hrs (in mg/m3) for Chlorine gas? Compare the value to gasoline, carbon
monoxide, and benzene.
MT-6 Whats in a Laboratory Glove?
64
Northeastern University Chemical Hygiene Plan see http://www.dac.neu.edu/oehs/lchpdoc.htm 1998.
117
gasoline vaporized exceeds the TLV of 300 ppm.65
Questions:
a) A spill of gasoline occurs such that a pool 0.6 meters in diameter is
formed in an area that has a ventilation rate of 85 m3/min. If the air
velocity is 2 m/s, what is the steady state concentration (in ppm) of
gasoline fumes in the enclosed area? Use a diffusivity of gasoline in air
of 1 X 10-5 m2/s and assume that the temperature is 25C and pressure is 1
atm. The vapor pressure of gasoline (MW=94) at 25C is 31,700 Pa.
A correlation to estimate the convective mass transfer coefficient is as
follows:66
jD = (kc / v) *(NSc)2/ 3 = 0.037NRe,
0.2
L
Where:
65
This MT-is a contribution from Prof. Ron Darby of Texas A&M University.
66
Perrys Chemical Engineers Handbook, 7th Ed., R.H. Perry and D.W. Green Editors McGraw Hill, New
York, 1997 p-5-59.
67
This MT-is a contribution from Prof. Ron Darby of Texas A&M University.
68
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed., Prentice
Hall Englewood Cliffs, NJ, 2002, p 89.
118
A is the surface area of the liquid from which the volatile is
releasing
Cppm is the concentration of the volatile in ppm
kc is the convective mass transfer coefficient
kmix is the nonideal mixing factor
M is the molecular weight of the volatile vaporizing
Psat is the vapor pressure of the volatile
P is the overall pressure
QM is the evolution rate of the material (mass per time)
Qv is the ventilation rate
Rg is the gas constant
TL is the temperature at the liquid surface (K)
Questions:
a) The effective ventilation rate for outside exposures has been estimated at
85 m3/min.69 A worker is standing near an open drum (D=0.6 m) of
toluene at 25C. Estimate the concentration for a non ideal mixing factor
of 0.1 to 0.5. The prevailing wind speed is 8 km/h.
A correlation to estimate the convective mass transfer coefficient is as
follows:70
Background: Source models are used to estimate release rates for pipes, hoses,
flanges, or tanks that may accidently rupture or leak. They provide useful
information for the evaluation of consequences of an unexpected leak such as
exposure (TLV estimation), fire (LFL estimation), or explosion potential (LEL
estimation). If the potential leaks are too severe, alternatives can be investigated
69
R. C. Matthiessen, Estimating Chemical Exposure Levels in the Workplace, Chemical Engineering
Progress, April, 1986, p. 30.
70
Perrys Chemical Engineers Handbook, 7th Ed., R.H. Perry and D.W. Green Editors McGraw Hill, New
York, 1997 p-5-59.
119
at the design stage to mitigate or to eliminate such leaks. Crowl and Louvar71
provide a number of source models for flow of liquids and vapors through a hole
and pipes. An example for estimation for flow of a liquid through a hole is
presented in this problem.
Questions:
a) Pure water at 26.1C is flowing at a velocity of 0.03 m/s inside a stainless
steel tube of 6.35 mm inside diameter. 72 Ten centimeters of this tube is
coated inside with benzoic acid. Estimate the outlet concentration of
benzoic acid. The solubility of benzoic acid in water is 0.02948 kg
mol/m3. The diffusivity of benzoic acid in water is 1.245 X 10-9 m2/s.
b) A 2mm diameter hole suddenly appears in the tubing. If the water
pressure inside the tube is 100 kPa gauge, what is the release rate, kg/s, of
the water-benzoic acid mixture into the environment? An equation to
estimate release rate of liquids through a hole is given below.73
Qm = ACo 2 Pg
Where:
Qm is the release rate in kg/s
A is the area of the hole, m2
Co is the orifice coefficient (use 0.61 unless otherwise known).
is the density, kg/m3
Pg is the gauge pressure in the pipe, Pa
Health and Safety Concept: Estimation of release rates for a broken gas line.
Background: Source models are used to estimate release rates for pipes, hoses,
flanges, or tanks that may accidently rupture or leak. They provide useful
information for the evaluation of consequences of an unexpected leak such as
exposure (TLV estimation), fire (LFL estimation), or explosion potential (LEL
estimation). If the potential leaks are too severe, alternatives can be investigated
at the design stage to mitigate or to eliminate such leaks. Crowl and Louvar74
71
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed., Prentice
Hall Englewood Cliffs, NJ, 2002, pp 109-170.
72
This MT-statement is very similar to those found in Geankoplis Example and MT-7.3-2.
73
D.A.Crowl and J.F. Louvar, pp 154.
74
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed., Prentice
Hall Englewood Cliffs, NJ, 2002, pp 109-170.
120
provide a number of source models for flow of liquids and vapors through a hole
and pipes. An example for estimation for isothermal flow of a gas through a pipe
is presented in this problem.
Questions:
a) A process operating in high vacuum requires an extremely low flow of
hydrogen for calibration purposes. Imagine that a 10mm long, 100
angstrom capillary is available. If the hydrogen pressure on the upstream
side of the capillary is 150 Pa and the temperature is 300 K , estimate the
flow of hydrogen (kg/s) through this novel metering system.
b) The hydrogen for the above process is being furnished through 1/8 OD
laboratory lines (wall thickness 0.021). The line break 5 meters from the
pressure regulator (set at 40 Psig). Estimate the flow of hydrogen into the
room in kg/s and m3/min. The following equation from Crowl and Louvar
can be used under the condition of isothermal choked flow.75 Assume that
this condition exists in this case with Pchoked = 101325 Pa (atmospheric
pressure).
c) What safety device could be added to the hydrogen laboratory supply line
MW
Q m ( kg / s ) = AP choked
RT
to prevent a fire from reaching the regulator and supply tank?
MT-11 A Puff
Health and Safety Concept: Toxic Release and Dispersion Models (Chapt 5.
Crowl and Louvar)
75
Adapted from D.A.Crowl and J.F. Louvar, pp 138.
76
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed.,
Prentice Hall Englewood Cliffs, NJ, 2002, pp 186-195.
121
Qm 1 x ut 2 y 2 z 2
C= exp + + 2
2 3/ 2 x y z 2 x y z
2
Where:
C is the conc, kg/m3 or kg mol/m3
Qm is the total release in kg or kg mol
x is the x direction orientated in the wind direction, m
u is the wind speed, m/s
i is dispersion coefficient, m. For stability Class C: Fx =Fy =
0.10x0.92, Fz=0.34x0.71 (x in m)
y is the distance from the center line of the wind vector, m
z is the height from ground level, m
t is the time, s
Questions:
a) Consider a sudden release of NH3 from a cooling system holding 200 kg
of NH3. If the local wind is blowing at 3 m/s, and day light gives a
stability similar to stability class C, plot the maximum concentration of the
puff as a function of x distance for a distance from 0.1 km to 1.0 km.
b) If the TLV of ammonia is 25 mg/m3, at what distance from the release
does the center concentration drop below the TLV?
c) Sometimes the best action in an event like this is to advise people to close
their doors and windows and stay inside until the cloud passes. How long
must people stay inside based on the answer found in part b?
MT-12 A Plume
Health and Safety Concept: Toxic Release and Dispersion Models (Chapt 5.
Crowl and Louvar)
77
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed., Prentice
Hall Englewood Cliffs, NJ, 2002, pp 186-195.
122
Qm 1 y2 1 z H 2 1 z + H 2
C= exp 2 X exp
r
+ exp r
2y zu 2 y 2
z 2
z
Where:
C is the conc, kg/m3 or kg mol/m3
Qm is the release rate in kg/s or kg mol/s
x is the x direction orientated in the wind direction, m
u is the wind speed, m/s
i is dispersion coefficient, m. For stability Class C: x =y = 0.11x(1
+ 0.0001x)-1/2, z=0.08x(1 + 0.0002x)-1/2 (x in m)
y is the distance from the center line of the wind vector, m
z is the height from ground level, m
Hr is the height of the stack from the ground, m (in this MT-assume
that the plume does not rise further above the top of the stack)
Questions:
a) A power plant is emitting 50 kg/h per of NO from a stack 40 m in height.
Estimate the NO concentration in ppb 500 m downwind from the power
plant. Prevailing wind that day is 3 m/s and the stability class is C.
b) Repeat the calculation in part a) for a position 100 meters off the
downwind centerline 500 m downwind at ground level. How does this
value compare to part a)?
c) What are some of the long-term exposure problems when children are
exposed to low concentrations of nitric oxide?
d) List three approaches used to control nitric oxide emissions from
stationary sources.
MT-13 A Chlorine Leak
78
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed. Prentice
Hall Englewood Cliffs, NJ, 2002, pp 186-195.
123
ground level.
Qm 1 x ut 2 y 2 z 2
C= exp
+ 2 + 2
2 3/ 2 x y z 2 x y z
Where:
C is the conc, kg or kg mol/m3
Qm is the total release in kg or kg mol
x is the x direction orientated in the wind direction, m
u is the wind speed, m/s
i is dispersion coefficient, m. For stability Class C: x =y =
0.10x0.92, z=0.34x0.71 (x in m)
y is the distance from the center line of the wind vector, m
z is the height from ground level, m
t is the time, s
Questions:
a) Consider a sudden release of chlorine from a tank truck that has tipped
over on an off-ramp from a major highway. The truck was carrying 5,000
kg of chlorine which all vaporized and formed a puff. The wind speed this
particular day is 2 m/s and is blowing in such a direction that a small town
is located 2,000 m directly downwind from the release. Plot the
concentration, mg/m3, due to chlorine at the center of this town as a
function of time starting with time=0 when the truck tips over until
time=60 minutes. Assume stability class C.
b) If the TLV of chlorine is 1.5 mg/m3, does the concentration of chlorine in
the center of the town ever exceed this amount?
c) How long do the officials have to warn people?
d) At what distance down stream does the maximum concentration stay
below the TLV-TWA for chlorine during the whole passage of the puff?
e) How long must people remain in their home?
Health and Safety Concept: Inherently safer processes and reportable quantities
124
limitation for mercury of 1.0 part per billion (ppb) from its regulated sources,
including hospitals and institutions.79 The rate of Hg dissolution into water is
governed by many factors (pH, external chemicals within the water like chlorine);
however, lets assume that it is proportional to dissolved oxygen and the intrinsic
surface reaction rate between mercury and that dissolved oxygen in water is given
by the following rate equation: 80 rate Hg (kg/m2 sec) = 1.2*10-5 * [dissolved
oxygen kg/m3]
Another concept covered in this MT-is reportable quantities. If an
accidental release or spill occurs of a hazardous substance above a reportable
quantity, it must be reported to appropriate authorities. These may include local
emergency planning committees (LEPC), state emergency response commissions,
or governmental agencies such as the EPA under the Superfund law (CERCLA).
Questions:
a) What is the diffusion coefficient for dissolved oxygen in water at 20C?
b) If the maximum solubility of oxygen in water is 9.1 mg/l at 20C and the
average coverage of the mercury by the water in a 2.5 cm diameter trap is
10 cm (the upper surface of the water is exposed to air and may be
assumed to be saturated), is the dissolution of Hg into the waste water a
surface reaction or a diffusion controlled process? Assume that 10 ml Hg
is exposed to the water as a hemisphere in the lower part of the trap.
c) Assuming that the rate of dissolution of Hg is reaction controlled, and that
this particular sink empties into a laboratory flow system that flows at an
average of 20 l/min, is this laboratory waste water in compliance with the
MWRA standards?
d) Inherently safer practice implies finding alternatives that are safer. List
some of the alternatives to mercury thermometers, manometers, and Hg
diffusion pumps.
e) What is the EPA reportable quantity for an accidental spill of mercury?
79
http://www.masco.org/mercury/
80
This equation has been created by the author for demonstration purposes only.
125
air in which a fire or combustion event can occur).
Auto-ignition Temperature (AIT): Temperature at which material will self ignite
(generally in air environments).
Questions:
a) A continuous flash distillation process is being used to split a 100 kg
mol/h of a 70/30 (by mol%) benzene/ toluene stream into a more
concentrated benzene stream. What are the predicted concentrations and
flow rates out of this flash unit, if it is run at atmospheric pressure and the
feed is 50 % vaporized (by mol%) before entering the unit?
b) What are the FP, LFL, UFL, and AIT for benzene and toluene
respectively?
c) When the unit starts up, what precautions should be taken to minimize a
fire?
MT-16 Flash Point Estimation of Mixtures
Background: The NFPA guidelines are often used to determine the amount of
flammables that can be stored in laboratories.81 Flammable liquids are divided
into three classes with Class I the most flammable and having three subcategories
(A,B,C). The classification uses flash points and vapor pressures to determine
the Class and Subclass. Quantities that can be stored within confined laboratory
space are then restricted for the more flammable liquids as judged by the flash
point. If the room has sprinklers, more flammable material can be stored. Pure
ethanol has a flash point of 55F and is classified as a Class 1 flammable (flash
point below 100F). Its quantity of storage quantity is thus restricted. However,
ethanol diluted with water will have a higher flash point and fall in a higher class
and thus more material can be stored. Flash point for water-miscible flammables
can be estimated using vapor pressure of the pure component and Raoults law.
Questions:
a) Construct the vapor-liquid equilibrium diagram for ethanol water (1 atm).
b) Using the McCabe Thiele Method, determine the number of ideal stages
needed for 90 wt% overhead and a 0.5 wt% bottom (ethanol) at total
reflux.
c) The feed for this unit is 15 wt% ethanol. Estimate its flash point in F.
See the reference below for a similar example with methanol-water.82
d) Note that the ethanol-water system is less ideal than the methanol-water
system. For extra credit, qualitatively discuss what is the effect of this
81
NFPA 45: Fire Protection for Laboratories Using Chemicals, NFPA Quincy Ma,
1982.
82
D.A. Crowl and J.F. Louvar, Chemical Process Safety: Fundamentals with Applications, 2nd ed. Prentice
Hall Englewood Cliffs, NJ, 2002, p 232.
126
non-ideal behavior. A process simulator may be used to assist in this
answer.
MT-17 Ammonia Absorption Tower
Where:
ED is the effective dose where a person begins to see an effect
(eyes water etc.).
TD is the toxic dose where long term illness may occur.
LD is the lethal dose where death will occur.
50 is the point where 50% of the population will be effected.
A method to model this data is the Probit Method84 in which the percentages are
transformed to a Probit variable (Y). A condensed table of percentages
transformed to Probits is as follows:
Percentage (%) 1 10 20 30 40 50 60 70 80 90 99
Probit, (Y) 2.67 3.72 4.16 4.48 4.75 5.00 5.25 5.52 5.84 6.29 7.33
Y = k1 + k2 ln V
Where k1 and k2 are constants determined from experience that match the
83
Ibid, p 48.
84
Ibid p 49.
127
causative variable V in consistent units. For example, the probit model can
estimate the number of people that would die if a group of people are exposed to a
1,000 ppm of ammonia in air for 2 minutes. In this case, the causative variable is
C2.75t where C is the concentration in ppm and t is time in minutes. For deaths
due to ammonia exposure, k1 = -30.57 and k2 = 1.385. k1 and k2 will vary
depending on the causative variable under examination (glass breakage, ear drum
rupture, death due to exposure in chlorine plumes etc). In the example above, we
can calculate Y and then estimate if any deaths will occur:
Y = -30.57 + 1.385 ln ( 1,000 ppm2.75 * 2 min) where V = C2.75t and Y = -3.3.
In this example the probit is below zero. Thus, the conclusion made is that no one
will die from this event. If Y = 5.00, then from Table 1, 50% of those exposed
would die.
Questions:
a) An ammonia absorption tower composed of 9.5 mm (3/8) Raschig Rings
has been proposed. The mass velocity of water will be set at 2.0 kg/s m2
and the ammonia stream entering (25 ppm of ammonia) will be set at a
mass velocity of 0.5 kg/s m2. Temperature of operation will be 30C.
Predict HG, HL, and Kya for this tower.
b) Imagine that one day the tower went out of service and personnel nearby
are exposed to 1,000 ppm of ammonia in air. How much time in minutes
would be available before 1 person in 100 dies?
Health and Safety Concept: Sizing of Rupture Disk for Gas Service (Chapt. 9
Crowl & Louvar)
( +1) /( 1)
g M 2
(Qm )choked = CoAPo c
R GT +1
Where:
Qm is the discharge flow rate through the rupture disk,
85
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.
Prentice-Hall, Englewood Cliffs, New Jersey, 2002, Chapt 9.
128
mass/time
Co is the orifice coefficient, use 1.0 for gases
A is the area of the rupture disk
Po is the upstream pressure (upstream pressure must exceed
the downstream pressure by 1.89 times for air to achieve
critical flow through the opening).
is the ratio of the heat capacities = 1.40 for air
M is the molecular weight
T is the temperature
RG is the universal Gas Constant
Questions:
a) A tray tower is to be designed for the absorption of SO2 from an air stream
using pure water at 293 K (68 F). The entering gas contains 1,000 ppm
SO2 and the exiting concentration of must be below 10 ppm. The normal
operating pressure will be 101.3 kPa. The air flow rate is set at 100 kg/hr
and the entering water is set at 2 times the minimum water required to
carry out the absorption process. Assuming that the actual trays are 50%
efficient, how many trays are needed? Equilibrium data for SO2- water
system can be found in Geankoplis A.3-19 p 885.
b) If the surrounding pressure around the column is atmospheric (101.3 kPa),
at what minimum pressure within the column would critical flow begin to
occur?
c) Using the pressure found in part b) and the design flow rate of air in part
a), what diameter rupture disk would be needed for this process unit?
MT-19 Ethanol-water Distillation and LOC
Health and Safety Concept: Inerting of process vessels to prevent fires (Ch. 7
Crowl and Louvar)
C C
Qvt = V ln 1 0
C2 C0
86
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.
Prentice-Hall, Englewood Cliffs, New Jersey, 2002, p 300.
129
Where:
Qv Flow rate of the inert
t Time
V Volume of system to be purged
C1 Concentration of oxygen in the unit before purging
C2 Concentration of oxygen in the unit after purging, for time t.
C0 Initial oxygen concentration in the inert stream.
LOC can be estimated by the following equation87:
Health and Safety Concept: Relief Vent Lines Piped to Flares and Flare Sizing
(Crowl & Louvar Ch. 8)
Background: Major refineries and chemical plants tie process vent lines and
relief vent lines from various processing units to flares. The function of flares is
to prevent releases of organic chemicals or toxic gases directly to the
environment. Instead these materials are combusted to inert products such as CO2
and water. A design criteria88 for flares is that the heat intensity at the base of the
flare not exceed 1,500 BTU/hr ft2. The effects of thermal radiation are detailed in
the following table (also from the same reference):
87
Ibid, p 238.
88
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002, p-375-376.
130
Heat Intensity Heat Intensity Effect
Btu/hr ft2 W/m2
2,000 6,300 Blisters in 20 seconds
5,300 17,000 Blisters in 5 seconds
3,000 to 4,000 9,450 to 12,600 Vegetation and wood
are ignited
350 1,100 Solar Radiation
Soen H. Tan in Hydrocarbon Processing, Jan 1967 derived the following equation
to estimate the safe height of flare towers to protect personnel who stay beyond a
certain distance from the flare.
4 q f X 2
960 Q m M
H t = 60 d t + 0 . 5 (120 dt)
2
t
q f
Where:
Ht is the flare height (ft).
dt is the diameter of the flare stack (ft)
qf is the heat intensity (Btu/hr/ft2)
Xt is the distance from the stack at grade (ft)
Qm is the vapor rate (lb/hr)
M is the molecular wt.
Questions:
a) A distillation tower with 10 trays is available for separation. The plant has
a need to separate a saturated vapor stream of 5,000 kg mol/hr of 60 mol%
benzene and 40 mol% toluene into a benzene-rich stream and a toluene-
rich streams. Using tray number 5 (from the top) as the feed tray, a reflux
ratio of 4.0, and a Murphree tray efficiency of 50%, determine the outlet
compositions for this tower.
b) Determine the height required of a 4 foot diameter flare tower that can
handle the feed stream in part a) given a heat intensity of 1,500 BTU/hr ft2
at a radius 400 ft from the base of the flare.
Health and Safety Concept: Static Electricity (Ch. 7.2 Crowl and Louvar)
89
Perrys Chemical Engineers Handbook, 7th Edition, R.H. Perry and D.W.Green Editors, McGraw Hill,
1997, p 26-70.
131
induction, and spraying. Contact electrification occurs when a contact is followed
by separation between solid-solid, liquid-solid, or liquid-liquid surfaces. A
typical example is the discharging of an organic liquid through a nozzle into a
tank. At the point of separation, electrons or ions flow from the nozzle to the
liquid (or visa versa), creating a charge accumulation in the liquid flowing into
the tank. Under certain circumstances, the charge build-up can be high enough to
create a spark and a fire may follow. Grounding and bonding of conductive
process equipment is a common mitigation method. As a rule of thumb, the
minimum conditions for a spark discharge are J>0.1 mJ and V>350 volts. If both
of these conditions exist, a spark may occur.
Crowl and Louvar present several equations and methods to estimate static
electricity concerns90. For exemplary purposes, the following equations are taken
from Crowl and Louvar (1st Edition):
The charge accumulated in filling a tank is:
Q = I s + (Qo Is )et /
And the maximum spark energy can be calculated by the following equation:
J = 0.5CV 2 = 0.5Q2 / C
Where:
Q is the charge in coulombs.
Is is the streaming current in amps (see Crowl and Louvar
Eqn. 7-12 and 7-14).
is the relaxation time (see Crowl and Louvar Eqn. 7-16).
t is the time from the initial addition of material into the
tank.
J is the total stored energy in joules.
V is the potential difference in volts.
C is the capacitance of the charged system in farads (see
Crowl and Louvar Eqn. 7-25).
When V exceeds 350 volts and J exceeds 0.1 mJ where flammables are present, a
spark may occur and the condition is considered dangerous91.
Questions:
a) A liquid-liquid extraction column is being designed for the separation by
liquid-liquid extraction of isopropanol from a hexane mixture by pure
water. The equilibrium data for this system are92:
90
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, Prentice-Hall,
Englewood Cliffs, New Jersey, 1990, pp 200-227
91
Ibid, p. 201.
92
Warning: although data are based from an actual experimental system; this data should not be used for
comparison or design purposes.
132
Light Phase (mass %) Heavy Phase (mass %)
IPA Hex. Water IPA Hex. Water
0.012 0.988 - 0.081 - 0.919
0.025 0.975 - 0.105 - 0.895
0.065 0.935 - 0.148 0.001 0.851
0.161 0.839 - 0.252 0.002 0.746
0.273 0.727 - 0.358 0.01 0.632
0.36 0.61 0.03 0.432 0.05 0.518
0.44 0.46 0.1 0.461 0.15 0.389
0.5 0.3 0.2 0.334 0.3 0.2
The entering hexane stream contains 0.15 mass fraction of IPA and no
water. The entering water stream is free of hexane and IPA. The desired
outlet stream is 0.01% IPA in hexane. If 1.5 times the minimum water is
used, and stage efficiency is 10%, how many stages are required for this
separation?
b) The tank containing the hexane stream holds 10,000 liters. Before the
process begins, the tank is filled at a rate of 100 liters per minute through
a 5 cm nozzle. Compute Q, V, and J for the tank just after filling if the
relaxation time is 1 X 105 seconds, Is is 1.5 X 10-13 amps, and the
capacitance is 3 X 10-10 farad. Is there a potential for a spark discharge?
c) What safety precautions should be taken when transferring flammable
materials in regard to minimizing fires due to static electricity?
d) (Extra Credit) Compare the values given for relaxation time, Is, and C for
part b) using the equations given in Crowl and Louvar. Treat the hexane
stream as pure hexane.
Health and Safety Concept: Relief Sizing (Crowl and Louvar Ch. 9).
Background: Relief valves are required for any line following a positive
displacement pump. This prevents line rupture or pump damage should the line
ever be blocked in by a closed valve downstream of the pump. Relief valves are
specified by the set pressure i.e., the pressure where the relief valve begins to
open. The set pressure is equal to the maximum allowable working pressure
(MAWP) or to 10% above the normal operating pressure (which must be below
the MAWP). As the pressure continues to increase beyond the set pressure
(called over-pressure), the relief valve opens more to a point where full relief
occurs (maximum over-pressure). For liquid flow, spring relief valve sizing can
be determined by the following equation93:
93
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p 385.
133
in2 ( psi)1/ 2 Qv ( / ref )
A=
38.0gpm Co Kv K p Kb 1.25PS Pb
Where:
A is the computed relief area (in2)
(/re) is the spec. gravity rel. to water
Qv is the volumetric flow through the relief (gpm) Ps is the set
pressure, psi
Co is the discharge coefficient Pb is the gauge back pressure, psi
Kv is the viscosity correction (Fig 9-2 Ref 32.)
Kp is the over-pressure correction (Fig. 9.3 Ref 32.)
Kb is the back-pressure correction (Fig.9-4 Ref 32.)
This equation assumes a maximum over pressure from set pressure of 25% (1.25
Ps). Kp corrects for maximum over pressures different from 25%.
Questions:
a) A reverse-osmosis membrane unit is to be used at 25C for a NaCl feed
solution containing 1.0 kg NaCl/m3. Preliminary experiments of the
membrane with a 10 cm2 area showed for a feed solution containing 10
kg/m3 of NaCl that the exit concentration across the membrane was 0.3 kg
NaCl/m3 with a measured flow rate of 2 X 10-8 m3/s. This test was done at
DP of 5 MPa. Feed flow rate was several orders of magnitude above the
product flow rate. Determine the solvent permeability (kg solvent/s m2),
and the solute permeability constant (m/s) for this membrane.
b) The proposed unit in part a) will be operated in the field at a DP of 3 MPa.
Calculate the water flux, solute flux and the solute rejection, R, for
operation of this unit.
c) The RO unit will operate at a pressure of 3 MPa gauge using a positive
displacement pump with a capacity of 5 gpm. What should the set
pressure be for a spring operated relief valve based on the information
given in the background? Assume that the MAWP for the pump, piping,
and unit is 4 MPa g.
d) Using the set pressure found in part c), what is the diameter of a spring
operated relief valve if Co =0.61, Kv=1.0, Kp=0.6, and Kb=1.0 and the back
pressure is 10 psi?
Health and Safety Concept: Deflagation Venting for Equipment Handling Dusts
(Ch. 9 Crowl & Louvar)
Background: The potential for dust explosions is present during milling and
processing of small particle solids. Occasionally, the first small explosion leads
134
to a second stronger explosion because the surrounding dust is displaced into the
environment during the first explosion. Control of dust explosions is handled
several ways including explosion suppression and proper venting of explosions.
Vent areas for low pressure structures (pressures below 1.5 psig, 10 kPa gauge)
can be estimated by the following equation94:
Cvent As
A=
P
Where Cvent is a function of the dust explosion class, St. The higher the St rating,
the more over-pressure that will occur upon an explosion95.
And
As is the internal surface area of the process vessel or the building
being vented.
P is the maximum over-pressure that can be withstood by the
weakest structural element.
Questions:
a) An organic-based material is processed in a through-circulation dryer as a
20 mm bed of 2-mm-diameter particles. The initial moisture content is
0.75 kg H2O/kg organic and the equilibrium moisture content is 0.02 kg
H2O/kg organic. The inlet air (0.5 m/s) has a humidity of 0.03 kg H2O/kg
dry air and a temperature of 120C. If the total critical moisture content is
0.4 kg H2O/kg organic, calculate the time for the particles to dry to 0.1 kg
H2O/kg organic. Take the bulk density of the bed to be 800 kg/m3 and the
solid density to be 1,600 kg/m3.
b) If the dryer in part a) is 2 m long, 1 m high, and 1 m wide, estimate the
proper vent size if the maximum over-pressure is 10 kPa gauge and the
material is an St-2 explosive class dust.
Health and Safety Concept: Risk Assessment (Ch. 11 Crowl and Louvar)
94
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p 407.
95
See NFPA 68, Venting of Deflagrations, NFPA, Quincy Ma for more details.
135
Background: Risk assessment includes scenario identification and consequence
analysis96. Frequently, equipment reliability and combined reliabilities of
redundant instrumentation is analyzed. The more a reliable a system is, the less
chance of an unexpected failure. Reliabilities are often modeled by the Poisson
distribution:
Reliability R(t) = e-mt where m is the failure rate (faults per year) and time is in
years. The failure probabilities, F, is equal to 1-R. When two independent
systems are involved, the reliability of the net process becomes:
n n
R = 1 (1 Ri ) = 1 Fi
i =1 i =1
Health and Safety Concept: Hazards Identification (Ch 10 Crowl and Louvar)
96
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p 474.
136
process. There are several methods that can be followed including process
hazards checklist, what-if analysis, Dow Fire and Explosion Index, hazard and
operability studies, and informal safety reviews. A typical process safety
checklist consists of a list of questions under the general categories of general
layout, building, process piping, equipment venting, instrumentation and
electrical safety equipment, and raw materials. An example is given in Fig. 10-2
of Crowl and Louvar97.
Questions:
A wastewater solution having a volume of 5 m3 contains 0.5 kg/m3 of a hazardous
chemical (HC). This solution is mixed thoroughly in a batch process with 5 kg of
a silica aerogel adsorbent until equilibrium is reached. Equilibrium isotherm data
for this system is as follows:
a) Fit the data to Langmuir and Freundlich isotherms. Which model fits the
data best?
Health and Safety Concept: Runaway Reactions and Relief Sizing (Ch 9 Crowl
and Louvar)
97
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed.,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p 433-436.
98
Ibid, p 433-437.
137
agitation has several times resulted in a runaway reaction and a subsequent
explosion.
Equations to estimate relief areas for two phase flow are based on data acquired
from the DIERS Vent Sizing Packages (VSP)99.
1 dT dT
q = Cv +
2 dt s dt m
Qm HV gc
GT = = 0.9
A fg CpTS
moq
A= 2
V H
GT V
+ CV T
mo fg
Notation:
q exothermic heat release per unit mass
Cv liquid heat capacity at constant volume
dT/dts heating rate at set pressure of relief
dT/dtm heating rate at max pressure of relief
GT mass flux through the relief
Qm is the release rate, mass/time
R correction factor for 2 phase flashing flow
)HV heat of vaporization of the fluid
<fg change in specific volume
Cp liquid heat capacity at constant pressure
Ts temperature of fluid at set pressure, absolute (K)
A required area for the relief system
mo mass of fluid within reactor before relief
V volume of liquid initially in the vessel
)T Temperature rise above set pressure
Questions:
a) A 6 m3 reactor is used to make a polymer by mixing two monomers. The
diameter of the reactor is 2 m and is filled to a height of 1 m with a
mixture of monomers A and B that has a solution viscosity of 15,000 cps.
If the density of the monomer mixture is 750 kg/m3 and the agitator (a 0.5
m pitched blade turbine operating at 50 rpm) is placed at the center of the
mixture, estimate the mixing time for this mixture.
99
Crowl, D.A. and Louvar, J.F. Chemical Process Safety: Fundamentals with Applications, 2nd ed,
Prentice-Hall, Englewood Cliffs, New Jersey, 2002. p 399, p 398.
138
b) VSP data from this system determined dT/dts = 0.5 K/s and dT/dtm = 0.65
K/s at a set temperature of 200C. Determine the relief diameter required
for this reactor if Lfg=0.08 m3/kg, Cp=2.5 kJ/kg K, =0.77, T=10 K, and
Hv=300 kJ/kg.
Level: Graduate Chemical Engineering (will require reading Louvar and Louvar
to complete the problem)
Health and Safety Concept: Consequence Analysis (Ch. 6 Louvar and Louvar)
100
Willey, R.J. The Bhopal Disaster, ISBN 0-8169-0766-8 SACHE-AIChE, New York, New York,
1999.
101
Louvar, J.F., Louvar, B.D., Health and Environmental Risk Analysis: Fundamentals with Applications,
Prentice Hall, Upper Saddle River, NJ, 1998.
139
Level: Undergraduate or Graduate
102
This problem is a contribution from Dr. Reed Welker, University of Arkansas.
140
pollution to the air. The hydrocarbon used for the extraction is the fuel oil for
process heaters. Equilibrium data for the acid-water-oil system are given in the
table below. Determine how much oil will be required to reduce the
concentration of acid from the 0.5 mass percent in the feed to 0.05 mass percent,
which has been found to be acceptable for discharge. The oil rate used in the
process will be 1.5 times the minimum, and the water to be treated will enter the
extraction system at a rate of 3500 gallons per day. The oil has a specific gravity
of 0.88. Assume the process is to be performed in a countercurrent liquid-liquid
extractor having an overall efficiency of 20 percent. How many stages will be
required for the extractor?
103
This problem is a contribution from Dr. Reed Welker, University of Arkansas.
141
(spring of 1989) indicates that cyclamates are not the carcinogens they were once
thought to be, and they may again be allowed to be used for artificial sweeteners.
It is usually much easier to determine a materials flammability
characteristics because no living organism needs to be tested to find the
properties. For example, the lower flammable limit (LFL) is the lowest
concentration at which a vapor or gas will ignite in air. Although the LFL
depends on the system temperature and to some lesser extent pressure, the most
obvious need is for data at ordinary ambient conditions. Thus, defining LFLs at
one atmosphere and room temperature provides sufficient data to use for
estimating danger of ignition. Such properties as the amount of energy released
during combustion are also easily measured. An ignition temperature is more
difficult to define and measure. For many materials, an ignition temperature
measured as the temperature at which a stoichiometric mixture of flammable
vapor and air begins a self-sustaining exothermic reaction has been determined.
It is called the auto-ignition temperature (AIT) and serves as an approximate limit
for determining when ignition will occur.
In order for a fire or deflagration to occur, there must be a fuel, an oxidizer,
and an ignition source such as a spark or a temperature high enough for ignition.
The ignition temperature is low enough for some materials that they will ignite at
ambient temperature or below when mixed. Such materials are said to be
hypergolic. Even materials that ignite only at temperatures several hundred
degrees above ambient are ignited by small amounts of energy, frequently less
than one millijoule. Most vapor-air mixtures can be ignited by the spark from a
static discharge, for example. Because of the ease of ignition and the rapid
combustion reaction that ensues, substantial rules and standards have been written
to define conditions for use of flammable materials. The standards of the
NATIONAL FIRE PROTECTION ASSOCIATION are available in most
libraries. They form the basis for many laws governing use of flammable
materials.
Whether a material is toxic or flammable or both, it must be kept well
confined if is to be used in commerce. The basic process design must account for
such materials and assure they are either used during the processes or destroyed
so they will not harm workers or the environment. Where it is possible, recovery
and recycling of chemicals is the best way of keeping them under control. If a
material is recycled, it will never be discharged to become a potential pollutant.
Questions: Benzene is used in a process as a solvent for a solid product, and it is
dried from the solid at the end of the process. Since benzene is quite flammable
(its LFL is 1.3 percent) and toxic (its permissible exposure limit is 10 parts per
million), nitrogen is recycled as a carrier gas during drying. Neither the nitrogen
nor the benzene is ever to be released from the process. In order to recycle both
the benzene (as a liquid solvent) and the nitrogen (as a carrier in the drying
process), the benzene in the nitrogen is stripped out in a tray absorber. The
benzene entering the absorber is at a concentration of 7.4 mole percent in
nitrogen. It must be reduced to a concentration of 0.4 mole percent in nitrogen,
after which the nitrogen stream will be heated and recycled to dry the product.
The benzene will be absorbed in an oil having a molecular weight of 200. The oil
enters the absorber at a rate of 0.5 moles of oil per mole of pure nitrogen entering
the absorber. Raoults law can be assumed to apply, and the absorber is designed
to operate at 50C (because the nitrogen-benzene stream entering is hot) and 1.0
atm. The vapor pressure of the oil is negligible, and the nitrogen can be assumed
142
to be insoluble in the oil. Determine the mole fraction of benzene in the liquid
leaving the absorption tower and the number of ideal trays required for the
process.
Background: Many common industrial materials will burn if they are ignited. In
order for ignition to occur, three criteria must be met. There must be fuel present,
there must be an oxidizer present, and there must be an ignition source. The fuel
is normally a gas or vapor, but it can also be a solid. Solids are particularly
dangerous if they are in small particles, or dusts. Almost all organic materials
will burn, frequently explosively, if they are finely divided enough. Liquid fuels
normally will have to be vaporized before they will burn, unless they are in the
form of fine droplets or mists. When we see a liquid pool burning, for example,
the fuel has first been vaporized and the vapor is burning. Gases can burn directly
once they are mixed with the oxidizer104.
The usual oxidizer for accidental fires is the oxygen in the air. Since
oxygen is nearly always available, fire prevention usually requires that the fuel is
kept in containment of some kind, so that if the fuel is a gas, it will not be able to
mix with air, and if the fuel is a liquid, it will not vaporize and then mix with the
air. There is a minimum concentration of fuel in air that is required for ignition.
It is called the lower flammable limit (LFL), and it is measured at atmospheric
pressure and ambient temperature. The LFL depends on temperature, and the
temperature effects can be estimated. However, unless the temperature range is
large, the effect is not usually important. Pressure has only minor effects on the
LFL unless the pressure change is substantial.
If a liquid is spilled, it will begin to vaporize. If the liquid is warm enough,
the equilibrium concentration of vapor above the liquid surface will be at or
greater than the LFL and it will be possible to ignite the liquid. Once a liquid
pool is ignited, it will normally continue to burn because sufficient energy will be
transferred from the flame back to the pool to vaporize additional fuel. The
concentration of fuel in the vapor phase will reach the LFL at a temperature that
is called the flash point. The flash point temperature is constant for any given
pure fuel, but if the fuel is a mixture, the flash point will be a function of the
composition of the fuel. There is also a minimum oxygen concentration (MOC)
that must be available for ignition to occur. Ignition is frequently prevented by
displacing the oxygen in the air above a liquid using nitrogen or carbon dioxide,
for example. Some fuels are soluble in water, and it is theoretically possible to
extinguish a fire burning in those fuels by diluting them with water. The reason
that the fire can thus be extinguished is that the mixture of water and fuel will
provide a lower vapor phase concentration of fuel than would a pool of pure fuel.
104
This MT-is a contribution from Dr. Reed Welker, University of Arkansas.
143
It is sometimes not possible or not desirable to extinguish a fire. In such a case,
the fire would simply be allowed to burn out. Or, put another way, the fire would
be extinguished when it ran out of fuel.
In the following problem we will explore some ways of looking at fires
and their extinguishment by adding water or by allowing the fuel to be exhausted.
y m = m x m P msat / P (1)
Where:
ym mole fraction methanol in the vapor
phase
xm mole fraction methanol in the liquid phase
m liquid phase activity coefficient
PSatm vapor pressure of methanol
P system pressure
The system temperature will be the bubble point temperature, which means that
for a binary system of water and methanol in equilibrium with air
Where:
yO2 mole fraction of oxygen
yN2 mole fraction of nitrogen
w subscript for the water component
m subscript for the methanol component
and:
xw 1 - xm
(3)
144
The temperature can be found by choosing a temperature (by trial and error) that
will satisfy Equation 2. Vapor pressure data can be obtained from a number of
sources. The following Antoine-type equations are good enough for our present
purposes.
ln(Pv/Pc) = A - B/(T + C)
(4)
WATER METHANOL
Health and Safety Concept: Pressure Relief (Ch. 9 Crowl and Louvar)
105
This problem is contributed by Prof. Chuck Sheppard, University of Tulsa, Tulsa, OK.
145
Questions:
Benzene and toluene are to be separated using distillation. The column operates
slightly above atmospheric pressure. Therefore, the overhead and bottoms
temperatures are around 177 and 232/F respectively. The reboiler transfers
energy from 15 psig steam (~250/F). The column is equipped with a pressure
relief device to remove excess energy in the case of a process upset or fire.
Consider the two cases below:
a) If the condenser coolant is lost and a tube in the reboiler breaks, what
would be the maximum pressure at the top? What determines the rate at
which vapor must be removed from the column? What is the maximum
cross-sectional area for flow?
b) If the condenser coolant is lost, what is the maximum temperature that can
be reached in the base of the distillation column (assuming infinite area)?
If the column only contained benzene, what would be the maximum
pressure at the top? Make a sketch of the reboiler duty and process
temperature with time. Hint: show the steam temperature and what
happens to the energy transfer rate as the driving force goes to zero.
Health and Safety Concept: Static Electricity (Ch. 7 Crowl and Louvar)
Background: When one walks across a carpet in the winter and touches a
grounded object a spark is discharged. The strength of this spark is enough to
ignite a flammable atmosphere. This occurs in the winter because of the low
humidity, when the humidity is high the water molecules in the air drain off the
electrons gathered from the carpet. Thus maintaining water content can be an
important safety consideration when there is rubbing of surfaces (e.g., flow or
other transport systems)106.
Questions:
Nylon fibers are being moved from one machine to another over rollers. The
process area is approximately 10'x10'x30'. The air is replaced by outside air 5
times per hour. The outside air is 40/F with a relative humidity of 50%. It is
planned to increase the humidity via mist from nozzles to 50% at the inside
temperature of 70/F Answer the questions below:
a) Where would you locate the spray nozzles?
b) How much air in ft3 and pounds are supplied per hour?
c) How much water do you supply an hour?
d) What is the furnace heat load assuming no other energy losses? Where
else would you lose energy; would these be significant?
106
This Problem is contributed by Prof. Chuck Sheppard, University of Tulsa, Tulsa, OK
146